Article pubs.acs.org/IC
Gallium(III) and Indium(III) Complexes with mesoMonophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of mesoPorphyrinylphosphonic Acid Monoester Yulia Yu. Enakieva,† Marina V. Volostnykh,†,‡ Sergey E. Nefedov,§ Gayane A. Kirakosyan,†,§ Yulia G. Gorbunova,*,†,§ Aslan Yu. Tsivadze,†,§ Alla G. Bessmertnykh-Lemeune,‡ Christine Stern,‡ and Roger Guilard*,‡ †
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Building 4, Moscow 119071, Russia ‡ Université de Bourgogne Franche-Comté, ICMUB (UMR CNRS 6302), 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France § Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991, Russia S Supporting Information *
ABSTRACT: The synthesis and structural characterization, both in solution by means of 1H and 31P NMR and UV−vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium(III) and indium(III) mesomono(diethoxyphosphoryl)porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium(III) cations of adjacent porphyrin molecules [Ga−O = 1.9708(13) Å].
■
INTRODUCTION The supramolecular chemistry of metalloporphyrins is an intensively developing area because of the growing needs in novel systems and materials with unique properties for applications in catalysis, optoelectronics, sensors, solar cells, biochemistry, medicine, etc. The nature of the central metals as well as the coordination ability of the peripheral functional groups and their number and arrangement on the porphyrin core significantly influence the architecture and properties of the self-organized assemblies.1−3 All complexes with metal ions capable of binding to an axial donor site are potentially powerful precursors for the development of supramolecular architectures through self-assembling processes. Among porphyrin complexes, those with the divalent metals, such as zinc(II) or magnesium(II), have been the most widely studied. More specifically, the investigation of the self-assembly of porphyrin derivatives containing trivalent metals is motivated by the fact that these complexes mimic the native iron(III)containing heme behavior.4−6 Indeed, the preparation of trivalent metal complexes with these biomimetic molecular systems, the investigation of the axial environment influence on the electronic properties of heme analogues, and their crystal structures are topics of © XXXX American Chemical Society
current interest to understand some natural molecular mechanisms and processes.7 The works of Bohle’s group have established that the substitution of iron(III) by gallium(III) or indium(III) cations provided useful models to elucidate the properties of iron(III) heme because of both the structural characterization of a gallium(III) protoporphyrin IX dimer and the possibility of using the diamagnetism of the gallium(III)/ indium(III) cations to investigate the solution dynamics of these complexes by NMR and fluorescence techniques.8−10 Both gallium(III) and indium(III) porphyrinates afford fiveand six-coordinate complexes. Indeed, it was shown that InIII(OEPO), where (OEPO)3− is the trianion of octaethyloxophlorin, is an oxygen-bridged dimer formed by the coordinative binding of the deprotonated meso-hydroxyl group to the indium(III) atom.11 Further, the cleavage of this indium(III) octaethyloxophlorin dimer with Lewis bases (imidazole, pyridine, etc.) to form supramolecular coordination complexes has been studied.12 In contrast, the gallium(III) protoporphyrinate IX gives an anionic dimer in the solid state through the intermolecular binding of the carboxylate groups of Received: December 30, 2016
A
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry Scheme 1
of two γ photopeaks and a long half-life, allowing increased manipulation time and complex purification steps without significant loss of activity. Despite this, its use has been largely superseded by the use of a positron-emitting 68Ga isotope for positron emission tomography, which allows an improved resolution and a reduced patient exposure to radiation with a short half-life.25 Altogether, these works demonstrate the large potential of gallium(III)/indium(III) porphyrins for developing new materials for optoelectronics, sensors, and medicine. The structural parameters of a porphyrin molecule should be carefully tailored in order to provide specific properties. Among the large amount of different functional groups introduced at the periphery of the porphyrin core, the phosphonate groups, which facilitate the construction of ordered molecular assemblies, attract much attention.26−29 Recent studies of metal(II) [zinc(II), magnesium(II), copper(II), and cadmium(II)] β- or meso-phosphoryl-substituted porphyrinates have shown that axial coordination of the phosphoryl oxygen atom of one porphyrinate molecule to the metal center of a neighboring molecule is a key factor responsible for the formation of supramolecular dimers as well as 1D or 2D coordination polymers.30−38 To the best of our knowledge, trivalent metal complexes with phosphorylated porphyrins have not been described so far. Herein, we report the design, synthesis, and characterization of novel indium(III) and gallium(III) complexes with meso(diethoxyphosphoryl)porphyrins bearing different peripheral substituents M-1a−M-1c and their corresponding monoesters M-2a and M-2b and M-3c and phosphonic acids M-4a−M-4c (Scheme 1). Single crystals of complexes In-1b and In-1c were
one propionate group of the porphyrin to the gallium atom of a neighboring macrocycle, while the second propionate group is involved in the formation of intramolecular hydrogen bonds.8 The presence of coordinated pyridine molecules, preventing the π−π stacking of porphyrin macrocycles, as well as the lack of intermolecular hydrogen bonding, lead to an increase in the dimer solubility in different organic solvents. This fact can be used for the development of drugs based on six-coordinate hematin anhydride analogues with trivalent metal, which inhibit the formation of malaria pigment.8 The self-assembly ability of gallium(III) or indium(III) porphyrins to form dimers via axial hydroxide-ion coordination has also been used to elaborate anion-selective sensing films.13−18 Trimeric species of gallium(III) porphyrins were also described.19,20 Only a few examples of polymeric structures formed by gallium(III) and indium(III) complexes with porphyrins are known. The photochemical oxidation of indium(III) porphyrins containing metal−sulfur bonds [InL(SR), with L = porphyrinate and R = alkyl or aryl] leads to sulfonato complexes that crystallize as 1D polymers.21 Moreover, a perturbed difference Fourier analysis of EXAFS spectra has shown that a fluorooctamethylporphyrinatogallium(III) derivative is a bridge-stacked polymer where a fluorine atom bridges two porphyrinic macrocycles.22 Recently, particular interest was paid to the synthesis and evaluation of gallium and indium porphyrins for their use in biomedical imaging applications.23,24 The stability of indium porphyrins makes them an attractive synthetic target to produce radiolabeled 111In derivatives. Use of the 67Ga isotope in γ imaging radiotracers is also an attractive prospect because B
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 1. 1H NMR spectra of Ga-1c in a CDCl3/CD3OD mixture (2:1, v/v) (a), CDCl3 (b), and toluene-d8 (c). Asterisks indicate signals of the residual of solvents and grease.
times) in order to remove the side products with subsequent drying under reduced pressure (10 mmHg) at 25 °C for 24 h. It should be noted that all attempts to obtain the gallium(III) complex Ga-2b through the reaction of free-base porphyrin 2H-2b with the corresponding metal salt (for the described conditions for Ga-1a−Ga-1c, see above) gave an inseparable mixture of gallium(III) porphyrinate (Ga-2b) and gallium(III) 5,15-ditolylporphyrinate (Ga-5b) (ratio ∼2:1 according to 1H NMR data; Figure S21 in the Supporting Information, SI). Complete hydrolysis of the diethyl ester of phosphonates M1 was achieved using trimethylsilyl bromide (TMSBr) according to the approach described previously.44−48 Treatment of the starting porphyrin Ga-1b, which was chosen as a model compound, with an excess of TMSBr in dry dichloromethane (CH2Cl2) resulted in the formation of Ga-5b bearing a bromine atom as an axial ligand (see the details in the SI, Xray structure part). C−P bond cleavage has already been observed for diethyl or diphenyl phosphonates under acidic conditions, and possible mechanistic pathways were postulated,49−53 but the detailed mechanism still requires further investigations. Meanwhile, the use of TMSBr for hydrolysis of In-1b led to the complete removal of metal atoms from the porphyrin macrocycle, as was observed previously for tetraazaporphyrins,54,55 and the partial hydrolysis of one ethyl group to give the free monoester of the meso-porphyrinylphosphonic acid 2H-2b. Nevertheless, the addition of triethylamine to the reaction mixture prevents C−P bond cleavage, and the formation of triethylammonium salts of Ga-4a−Ga-4c and In-4a−In-4c after the addition of MeOH occurs in quantitative yields.
also investigated in the solid state by X-ray diffraction. Moreover, the X-ray structure of the dimer, formed by the self-assembly of monoester Ga-2b through the axial interaction of anionic oxygen atoms of the meso-porphyrinylphosphonic acid monoester groups and gallium(III) cations of adjacent porphyrin molecules, is described for the first time.
■
RESULTS AND DISCUSSION Synthesis of Gallium(III) and Indium(III) Phosphorylated Porphyrins. Metalation was performed using a published synthetic procedure.39−42 Porphyrins 2H-1a−2H1c obtained from the corresponding zinc complexes43 were reacted with metal salts in boiling acetic acid in the presence of sodium acetate for 20 min to afford the corresponding complexes Ga-1a−Ga-1c and In-1a−In-1c in quantitative yield (Scheme 1). Next, these complexes M-1 were subjected to alkaline hydrolysis to prepare the corresponding monoesters M-2 and M-3 (Scheme 1). The reaction proceeded smoothly in a tetrahydrofuran (THF)/methanol (MeOH) (2:1, v/v) mixture containing a 0.5 M sodium hydroxide (NaOH) solution in H2O under reflux for 1 day. Treatment of the reaction mixtures with 0.5 M HCl followed by column chromatography afforded the target products M-2a and M-2b in quantitative yield. In the meantime, the simultaneous hydrolysis of a carbomethoxy group to a carboxy group was observed in the case of M-1c compounds. Because of the presence of both carboxy and phosphonic acid monoester groups in M-3c, such compounds were insoluble in organic solvents; therefore, their purification included washing of the reaction mixture with H2O (2 times) and acetone (2 C
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 2. Variable-temperature 1H NMR spectra of In-3c (aromatic region) in D2O in the presence of 1 drop of a saturated solution of NaOH in D2O.
and S5 in the SI), but no resonance signals of the axial ligand protons were observed. Taking into account the existence of dynamic processes in a CDCl3/CD3OD solution, the lack of an axial ligand signal can be explained by rapid exchange on the NMR time scale in the presence of CD3OD. Thus, NMR spectra of Ga-1a−Ga-1c were recorded in CDCl3 and toluened8 in order to detect the signal of the axial ligand protons (Figures S14b,c−S16b,c in the SI). The comparison of 1H NMR spectra in different solvents is shown for compound Ga1c as an example (Figure 1). The signal corresponding to the axial acetate ion appears as a singlet at −0.72 ppm in CDCl3 and toluene-d8 in accordance with the literature data.42 The signal is strongly upfield-shifted because of the shielding effect of the porphyrin backbone. The same signal was observed in 1H NMR spectra of complexes Ga-1a and Ga-1b at −0.75 and −0.78 ppm, respectively. In addition, for all of the compounds, the broadening and splitting of signals of some protons are observed in both chloroform and toluene (c ∼ 10−3 M) at ambient temperature, resulting from an aggregation phenomenon due to slow exchange between monomeric and aggregated forms (Figures S14b,c−S16b,c in the SI). The comparison of the 31P NMR spectra of solutions of Ga1a−Ga-1c in different solvents also proves the existence of aggregation of monomers moving from a CDCl3/CD3OD mixture to a CDCl3 and toluene-d8 solution (Figures S17a-c− S19a-c in the SI). Indeed, additional broad phosphorus signals are observed in 31P NMR spectra of CDCl3 and toluene-d8 solutions.
The obtained soluble complexes Ga-1a−Ga-1c, In-1a−In1c, Ga-2a, Ga-2b, In-2a, In-2b, 2H-2a, 2H-2b, and Ga-5b were isolated using chromatography on silica gel (see the Experimental Section). Characterization in Solutions. All obtained gallium(III) and indium(III) porphyrinates were characterized in solution by 1H and 31P NMR and UV−vis spectroscopies as well as high-resolution mass spectrometry (HRMS; electrospray ionization, ESI) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF MS; see the Experimental Section and SI). Only ions with m/z values corresponding to complexes without an axial ligand were observed for compounds Ga-1a− Ga-1c, In-1a−In-1c, Ga-2a, Ga-2b, In-2a, and In-2b in HRMS spectra. In contrast, use of MALDI-TOF MS in the case of indium complexes (In-1a−In-1c) makes it possible to detect molecular ions with m/z values corresponding to indium(III) porphyrinates bearing chloride as an axial ligand. In view of the reagents and solvent nature used for gallium(III) porphyrinate synthesis, as well as purification conditions, complexes Ga-1a− Ga-1c can bear different axial ligands that could be sulfate, acetate, or hydroxyl groups. Because MS was found to be a noninformative method for determination of the composition of gallium(III) complexes Ga-1a−Ga-1c, the nature of the axial ligand in these complexes was studied by NMR techniques. The 1 H NMR spectra of gallium(III) porphyrinates Ga-1a−Ga-1c in a deuterated chloroform (CDCl3)/deuterated methanol (CD3OD) mixture (2:1, v/v) were in accordance with the proposed structures of the compounds (Figures 1 and S1, S3, D
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry Table 1. UV−Vis Spectroscopic Data of Complexes in CHCl3/MeOH (1:1) Solutions λmax, nm (log ε) compound Ga-1aa Ga-1bb Ga-1ca In-1aa In-1ba In-1ca 2H-2a 2H-2bb 2H-3c Ga-2ac Ga-2bc Ga-3cc In-2ac In-2bc In-3cc Ga-4ac Ga-4bc Ga-4cc In-4ac In-4bc In-4cc Ga-5ba
Soret bands 414 417 416 420 420 420 412 415 414 412 414 416 416 420 420 412 414 414 416 420 420 410
(5.26) (5.45) (5.42) (5.38) (5.46) (5.39) (5.18) (5.45) (5.44) (5.53) (5.36) (5.57) (5.36) (5.13) (5.63) (5.42) (5.54) (5.65) (5.11) (5.27) (5.53) (5.47)
Q bands 546 547 548 554 554 552 510 511 510 546 546 548 552 554 554 546 548 548 552 554 556 540
(4.15) (4.20) (4.13) (4.28) (4.17) (4.08) (3.98) (4.32) (4.28) (4.22) (4.10) (4.28) (4.16) (3.92) (4.38) (4.20) (4.30) (4.44) (3.95) (4.11) (4.47) (4.21)
584 584 584 588 586 588 542 542 542 580 582 584 586 592 594 584 584 586 586 592 592 578
(3.92) (3.91) (3.89) (4.11) (3.88) (3.71) (3.78) (3.94) (3.78) (3.68) (3.65) (3.78) (3.71) (3.57) (3.78) (3.71) (3.68) (3.83) (3.61) (3.70) (3.84) (3.66)
582 (3.83) 585 (3.99) 584 (3.92)
634 (3.61) 637 (3.34) 636 (3.60)
a The spectra were recorded in a CHCl3 solution. bThe spectra were recorded in a CHCl3/MeOH mixture (95:5, v/v). cThe spectra were recorded after the addition of 1 drop of saturated NaOH in H2O to the solution of compounds in a CHCl3/MeOH mixture.
meso proton. The morphology of the room temperature spectra enables the suggestion that the complex molecules in aqueous alkaline solutions are aggregated. It is reasonable to assume the formation of a dimer structurally similar to iron(III) and manganese(III) complexes with 5-(2-hydroxyphenyl)-10,15,20tris(p-tolyl)porphyrin obtained under basic hydrolytic conditions.56,57 In order to confirm this issue, variable-temperature NMR spectra were measured. Really, the 1H NMR spectra of the gallium(III) and indium(III) complexes at 353 and 363 K were the wellresolved spectra of the corresponding monomers (Figures 2 and S34 in the SI). All of the signals were assigned from the 2D NOESY NMR experiments carried out at 353 and 363 K for the gallium and indium complexes, respectively (Figures S36 and S38 in the SI). According to Figure 2, increasing temperature leads to a downfield shift of all proton resonances and the appearance of additional signals with a noticeable improvement in their resolution. For the indium complex as an example, the temperature-induced downfield shift of the signals of the protons of the pyrrole rings adjacent to the phosphoryl substituent and those of the signals of the phenyl protons is about 0.7 ppm, while the shift for the pyrrole protons adjacent to the meso proton is, on average, 1.0 ppm and that for the meso proton itself is even larger, being 1.2 ppm. The considerable upfield shift and changes in line shapes of the signals of the meso proton and the pyrrole protons located in the unsubstituted part of the porphyrin ring in the spectra at room temperature indicate that the corresponding protons are subjected to the ring-current effect of the porphyrin π system. These data suggest the involvement of these protons in selfassembling processes. On the contrary, negligible temperatureinduced changes in line shapes of the signals in the 1H NMR spectra of complexes Ga-3c and In-3c for the portion of the
The NMR spectra of indium compounds In-1a−In-1c are, in general, similar to those of the gallium(III) derivatives (Figures S8−S13 and S20 in the SI). However, in contrast to the gallium(III) compounds, an additional upfield-shifted signal around −0.7 ppm is not observed for the indium complexes; this result is in good accordance with MALDI-TOF MS and Xray diffraction data, which demonstrate the presence of a chloride anion as an axial ligand (see below). Gallium(III) and indium(III) complexes Ga-2a, Ga-2b, Ga3c, In-2a, In-2b, and In-3c exhibit a low solubility in common organic solvents and H2O probably because of self-assembling processes resulting in the formation of polymers through strong interaction between anionic oxygen atoms of meso-porphyrinylphosphonic acid monoesters and metal(III) cations of adjacent porphyrin molecules. In the meantime, the addition of NaOH in deuterated H2O (D2O) to a solution of compounds in a CDCl3/CD3OD mixture suppresses the self-assembly and allows the characterization of complexes by NMR, which proves their structures (Figures S22−S33 in the SI). It is worth noting that, for complexes Ga-3c and In-3c, solutions in a CDCl3/CD3OD mixture with the addition of NaOH in D2O were slowly layered while the spectra were recorded, and the colored complexes were extracted into the aqueous phase. Therefore, the 1H NMR spectra of these compounds dissolved directly in D2O with the addition of 1 drop of a saturated solution of NaOH in D2O were measured at 298 K. The spectra showed two sets of signals: four somewhat broadened partially resolved multiplets and a few much more broadened featureless signals (Figures 2 and S34 in the SI). The COSY NMR spectra at room temperature (Figures S35 and S37 in the SI) showed cross-peaks between pairs of narrow signals, which allowed us to assign them to four pyrrole and all phenyl protons. However, the spectra of both complexes lacked pronounced signals of the remaining pyrrole protons and of the E
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 3. Molecular structure of complex In-1b (a) and crystal packing (b). Displacement ellipsoids are drawn at the 30% probability level; hydrogen atoms are omitted for clarity.
compared to the pyrrole protons adjacent to the meso proton. It is likely that such a self-assembly mode is a characteristic feature of the behavior of this ligand, containing an unsubstituted meso proton, in an alkaline aqueous solution. The MALDI-TOF MS spectra of gallium(III) mesoporphyrinylphosphonic acids Ga-4a−Ga-4c contain signals of molecular ions of the monomers or its dimeric form without axial ligands in good agreement with the calculated exact masses of the corresponding derivatives (Figures S65−S67 in the SI). Again, molecular ions with axially coordinated bromine atoms were registered for In-4a and In-4b, allowing confirmation of the structures of these compounds (Figures S68 and S69 in the SI). Similar to monoesters, porphyrinylphosphonic acids are almost insoluble in organic solvents or H2O due to self-assembly. Therefore, the 1H NMR spectra of complexes Ga-4a−Ga-4c and In-4a−In-4c were also recorded in the presence of NaOD. The signals of protons corresponding only to the porphyrin core and the peripheral substituents of the phenyl rings were observed, indicating complete hydrolysis of both ethyl groups of the phosphoryl moiety (Figures S47− S58 in the SI). It should also be noted that the 31P resonance in the NMR spectra of all gallium(III) and indium(III)
molecule adjacent to the meso-porphyrinylphosphonate substituent enable the conclusion that this moiety is not involved in the aggregation phenomenon. This is consistent with the fact that the presence of sodium cations in aqueous solutions of both complexes could preclude self-assembly through strong interaction between the anionic oxygen atoms of mesoporphyrinylphosphonic acid monoesters and the metal(III) cations of the neighboring porphyrin molecules. On the other hand, the molecular structures of these compounds can also favor aggregation through the π−π stacking of porphyrins or the formation of numerous hydrogen bonds between porphyrin protons and solvent molecules. It is likely that the gallium and indium atoms in Ga-3c and In-3c are not involved in this process. In an attempt to prove or refute the minor role of the metal in the observed self-assembly, analogous NMR experiments were carried out for a solution of free ligand 2H-3c in D2O with the addition of NaOH (Figures S45 and S46 in the SI). Although there are differences caused by the less symmetric structure of free ligand molecules, it is possible to highlight the same trends in the temperature-induced behavior of the 1H NMR spectra: the pair of pyrrole protons adjacent to the phosphoryl substituent are much less prone to association F
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 4. Molecular structure of complex [In-1c]2. Displacement ellipsoids are drawn at the 30% probability level; hydrogen atoms are omitted for clarity.
Single crystals of In-1b and In-1c were obtained at 25 °C upon slow diffusion of hexane into a CHCl3 solution of indium(III) porphyrinates. The molecular structure of In-1b is shown in Figure 3. The indium(III) atom adopts a squarepyramidal geometry. Its coordination sphere is composed of four nitrogen atoms of the porphyrin core [In−N distances in the 2.140(8)−2.171(6) Å range] and the chlorine atom occupying the apical position [In−Cl distance is 2.372(2) Å]. The In−N distances are comparable to those determined for indium(III) complexes with 5,10,15,20-tetraphenylporphyrin,58,59 2,3,7,8,12,13,17,18-octaethylporphyrin,60 5,10,15,20tetra(pentafluoro)phenylporphyrin, and 2,3,8,13-tetrachloro5,10,15,20-tetraphenylporphyrin,61 which contain a chloride anion as an axial ligand. The indium atom is displaced out of the N4 plane by 0.607 Å toward the chloride ligand, with the porphyrin ring exhibiting a slight saddle distortion. The degree of deformation and structural metrics are close to those previously reported for indium(III) porphyrin complexes. The angle between the N1/In1/N2 and N3/In1/N4 planes is 44.66°, and the displacement of the four pyrrole N4 atoms from the mean porphyrin plane is 0.104 Å toward the chlorine atom. The displacement of the pyrrole carbon atoms varies from 0.080 to 0.213 Å. The meso substituents are tilted with respect to the porphyrin mean plane with C−C−C dihedral angles of 116.55° and 116.75°. The phosphorus atom of the phosphoryl substituent lies on the same side of the macrocycle as the chloride ligand at a distance of 0.281 Å from the N4 plane. The P1−O1 distance is 1.452(6) Å, P1−O2 is 1.588(8) Å, and P1−O3 is 1.536(8) Å. The dihedral angle between the C4/C5/C10 and C5/P1/O1 planes is 63.54°. In the crystal
compounds is upfield-shifted when going from diesters Ga-1a− Ga-1c and In-1a−In-1c (∼22 ppm) through monoesters Ga2a, Ga-2b, Ga-3c, In-2a, In-2b, and In-3c (∼14 ppm) to phosphorylphosphonic acids Ga-4a−Ga-4c and In-4a−In-4c (∼11 ppm). The UV−vis absorption spectra of the solutions of all synthesized compounds were also investigated. The spectra are typical of porphyrin derivatives and contain an intense Soret band and four Q bands for free-base ligands, which are transformed into two Q bands after the insertion of metal ions (Table 1). It was earlier demonstrated that UV−vis absorption spectroscopy could be used to estimate the ability of some polyphosphorylporphyrins to self-assemble in solution.30,33,34 Unfortunately, no evidence of the aggregation of In-1a−In-1c and Ga-1a−Ga-1c in a CHCl3 solution over a compound concentration range of 10−7−10−4 M has been observed by means of UV−vis spectroscopy. Because of the low solubility of monoesters and porphyrinylphosphonic acids, the UV−vis spectra were recorded only in the presence of sodium cations, preventing aggregation. Attempts to investigate the temperature-induced association of a monoester in an aqueous solution of In-3c as an example were also unsuccessful. Apparently, at working concentrations required for the correct recording of UV−vis spectra and temperatures above 273 K, it is rather difficult to identify the formation of aggregates. Single-Crystal X-ray Structure. Complexes In-1b, In-1c, Ga-2b, and Ga-5b were also studied by single-crystal X-ray diffraction (see the crystallographic part in the SI, Table S1, and for relevant bond distances and angles, see Tables S2−S5 in the SI). G
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 5. Molecular structure of complex [Ga-2b]2·2py. Displacement ellipsoids are drawn at the 30% probability level; hydrogen atoms are omitted for clarity.
packing of In-1b, there are no remarkable intermolecular contacts (Figure 3b). In contrast to complex In-1b, complex In-1c bearing 4carbomethoxyphenyl meso substituents crystallizes as mutually coordinated dimers in which two laterally shifted cofacial porphyrin molecules are bonded through two coordinative P− O···In bonds (Figure 4). The indium atom is located in the center of the macrocycle and is coordinated to four nitrogen atoms of the porphyrin core [In−N 2.115(7)−2.148(7) Å]. The axial positions in the octahedral environment of the indium atom are occupied by the chlorine and oxygen atoms of the phosphonate substituent of a neighboring porphyrin molecule [In−O 2.423(6) Å; In−Cl 2.500(3) Å]. The displacement of the indium atom from the N4 plane toward the chlorine atom is 0.259 Å, which is more than 2 times shorter than that observed for In-1b. The slight distortion of the porphyrin core leads to the displacement of the pyrrole carbon atoms either upward or downward from the mean N4 plane from −0.249 to +0.211 Å. The meso substituents are tilted with respect to the porphyrin mean plane with C−C−C dihedral angles of 118.01° and 115.97°. The phosphorus atom of the phosphoryl substituent lies on the same side of the macrocycle as the chloride ligand at a distance of 0.023 Å from the N4 plane; the P/O/In angle is 145.7(4)°. The P−O distances are 1.475(6), 1.572(6), and 1.575(6) Å. These data are in good agreement with those observed for the zinc(II) dimer formed through the PO···Zn bond [the P−O distances 1.478(3), 1.580(4), and 1.579(3) Å].30 The dihedral angle between the C1/C36/C35 and C36/P1/O1 planes is 65.68°. Laterally shifted cofacial porphyrin molecules in the dimer are partially overlapped so that the ester moiety and two adjacent pyrrole units of one macrocycle are located above the second porphyrin ring. The distance 3.411 Å between two parallel porphyrin planes corresponds to standard π−π-stacking interactions. Thus, the dimer is formed through two coordination bonds and stabilized by an additional π−π stacking. The distance between two indium atoms is 6.915 Å. CHCl3 molecules are present in the crystal structure as solvates. Two chlorine atoms of one CHCl3 molecule have contacts with
the axial chloride ligand Cl1···Cl2CHCl3 (3.432 Å) and the hydrogen atom of the ethyl group of the phosphoryl moiety, H40B−Cl4CHCl3 (3.063 Å). Because of the low solubility of monoester Ga-2b in CHCl3, single crystals of Ga-2b suitable for X-ray diffraction were grown from a pyridine/MeOH/CHCl3 mixture (1:1:1) at 25 °C upon slow evaporation in a glass tube for 1 week. The solid structure of [Ga-2b]2·2py is shown in Figure 5. The compound is self-organized into a head-to-tail dimeric structure, with the meso-phosphonate groups forming bridges between one macrocycle and the metal center of the adjacent molecule. Indeed, one of the oxygen atoms of the phosphonate substituents is involved in the formation of an axial coordinative bond with a metal cation. The Ga−O bond length in [Ga-2b]2· 2py is 1.9708(13) Å, which is comparable to that in the propionate-bridged gallium(III) protoporphyrinate dimer8 and (tetraphenylporphyrinato)gallium(III) acetate,62 exhibiting Ga−O distances of 2.010(3) and 1.874(4) Å, respectively. Both gallium(III) atoms are six-coordinate and adopt an octahedral geometry, being bonded (in addition to the phosphonate oxygen atom) to four nitrogen atoms of the porphyrin core [Ga−N distances are within 2.0258(15)− 2.0362(16) Å] and one pyridine molecule, which occupies an axial position [Ga1−N5 2.2016(17) Å]. The porphyrin core has partially ruffled distortion (the displacement of the carbon atoms of pyrrole either upward or downward from the mean N4 plane is from −0.190 to +0.206 Å), and gallium is 0.074 Å out of the N4 plane toward the oxygen atoms. The P−O distances are 1.5129(13) Å (P−O1), 1.4720(15) Å (PO2), and 1.6055(14) Å (P−O3). The dihedral angle between the C21A/ C22A/C23A and C22A/P1/O1 planes is 49.3°. The distance between the porphyrin planes in Ga-2b is 3.269 Å, and the Ga···Ga separation is 6.450 Å, which are considerably shorter than those in gallium(III) protoporphyrin IX [Ga(PPIX)(py)]2,5 where the plane separation is 4.651 Å and the distance between the metal centers 8.199 Å. As mentioned above, the attempt to hydrolyze complex Ga1b using an excess of TMSBr resulted in the formation of the H
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
structure factor calculations in the riding motion approximation. All of the data reduction and further calculations were performed using the SAINT and SHELXTL program packages.66,67 CCDC reference numbers are 1519794−1519797. The data can be obtained free of charge from the Cambridge Crystallographic Data Centre at www. ccdc.cam.ac.uk/data_request/cif. Synthesis. The starting compounds [10-(diethoxyphosphoryl)5,15-diphenylporphyrinato(2−)]zinc(II) (Zn-1a), [10-(diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato(2−)]zinc(II) (Zn-1b), [10-(diethoxyphosphoryl)-5,15-bis{4-(methoxycarbonyl)phenyl}porphyrinato(2−)]zinc(II) (Zn-1c), and 10-(diethoxyphosphoryl)5,15-diphenylporphyrin (2H-1a) were prepared according to published procedures.43 General Procedure for the Preparation of 10-(Diethoxyphosphoryl)-5,15-diarylporphyrins (2H-1b and 2H-1c). To a solution of the corresponding zinc complex Zn-1 in CHCl3 (1 mmol/L) was added an aqueous solution of hydrochloric acid (4 M), and the reaction mixture was vigorously stirred. The progress of the reaction was monitored by MALDI-TOF MS spectrometry. Upon completion of demetalation (3 h), the reaction mixture was washed with a saturated aqueous sodium carbonate solution and with H2O (two times). The organic phase was dried with anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The resulting crude solid was purified by column chromatography on silica gel using a CHCl3/hexane mixture (1:1, v/v) as an eluent. Combined colored fractions were evaporated under reduced pressure to afford 2H-1. 10-(Diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrin (2H-1b). The compound was prepared from Zn-1b (0.050 g, 0.070 mmol) by treatment of an aqueous solution of hydrochloric acid (0.3 mL) in CHCl3. The porphyrin 2H-1b was obtained in 90% yield (0.041 g) as a violet solid. 1H NMR (600 MHz, CDCl3, 25 °C): δH 10.36 (bs, 2H, Hβ), 10.20 (s, 1H, Hmeso), 9.25 (d, 3JH,H = 4.3 Hz, 2H, Hβ), 8.97 (d, 3 JH,H = 4.8 Hz, 2H, Hβ), 8.89 (d, 3JH,H = 4.8 Hz, 2H, Hβ), 8.07 (d, 3JH,H = 7.8 Hz, 4H, o-Ph), 7.57 (d, 3JH,H = 7.8 Hz, 4H, m-Ph), 4.52−4.45 (m, 2H, CH2O), 4.23−4.17 (m, 2H, CH2O), 2.72 (s, 6H, CH3), 1.32 (t, 3JH,H = 7.0 Hz, 6H, CH3), −2.79 (s, 2H, NH). 31P NMR (600 MHz, CDCl3, 25 °C): δP 23.2. MS (MALDI-TOF). Calcd for C38H36N4O3P ([M + H]+): m/z 627.25. Found: m/z 627.63. HRMS (ESI). Calcd. for C38H36N4O3P ([M + H]+): m/z 627.25195. Found: m/z 627.25355. UV−vis [CHCl3/MeOH, 97:3, v/v; λmax, nm (log ε)]: 418 (5.40), 516 (4.13), 550 (3.75), 588 (3.72), 640 (3.59). IR (neat, cm−1): νmax 3320 (w, NH), 2960 (w), 2920 (w), 2852 (w), 1550 (w), 1508 (w), 1442 (w), 1390 (w), 1248 (w, PO), 1227 (w, PO), 1210 (w, PO), 1182 (w), 1163 (w), 1093 (w), 1036 (s), 1015 (s, P−O), 950 (s, P−O), 941 (s), 884 (m), 870 (m), 857 (m), 837 (m), 791 (s), 781 (s), 737 (s), 722 (s), 692 (m), 638 (w). 10-(Diethoxyphosphoryl)-5,15-bis{(4-(methoxycarbonyl)phenyl}porphyrin (2H-1c). The compound was prepared from Zn-1c (0.050 g, 0.064 mmol) by treatment of an aqueous solution of hydrochloric acid (0.26 mL) in CHCl3. The porphyrin 2H-1c was obtained in 92% yield (0.042 g) as a violet solid. 1H NMR (600 MHz, CDCl3, 25 °C): δH 10.40 (bs, 2H, Hβ), 10.26 (s, 1H, Hmeso), 9.30 (d, 3JH,H = 4.3 Hz, 2H, Hβ), 8.88 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 8.82 (d, 3JH,H = 4.3 Hz, 2H, Hβ), 8.46 and 8.28 (AB system, JAB = 8.1 Hz, 8H, m-Ph and o-Ph, respectively), 4.54−4.46 (m, 2H, CH2O), 4.24−4.18 (m, 2H, CH2O), 4.12 (s, 6H, CH3), 1.33 (t, 3JH,H = 7.0 Hz, 6H, CH3), −2.85 (s, 2H, NH). 31P NMR (600 MHz, CDCl3, 25 °C): δP 22.5. MS (MALDITOF). Calcd for C40H36N4O7P ([M + H]+): m/z 715.23. Found: m/z 715.69. HRMS (ESI). Calcd for C40H36N4O7P ([M + H]+): m/z 715.23161. Found: m/z 715.22826. UV−vis [CHCl3/MeOH, 97:3 v/ v; λmax, nm (log ε)]: 416 (5.52), 510 (4.35), 542 (3.79), 584 (3.90), 636 (3.62). IR (neat, cm−1): νmax 3325 (w, NH), 2983 (w), 2920 (w), 2850 (w), 1720 (w), 1606 (m), 1550 (w), 1432 (m), 1402 (m), 1276 (s, PO), 1249 (s, PO), 1227 (w, PO), 1190 (w), 1167 (w), 1098 (m), 1040 (s), 1017 (s, P−O), 953 (s, P−O), 885 (m), 864 (m), 796 (s), 750 (s), 738 (s), 710 (m), 691 (m). General Procedure for the Preparation of [10-(Diethoxyphosphoryl)-5,15-diarylporphyrinato(2−)](acetato)gallium(III) (Ga-1a− Ga-1c). A 3.4 mM solution of the corresponding free base porphyrin 2H-1, gallium(III) sulfate (3 equiv), and sodium acetate (30 equiv)
complex Ga-5b. Single crystals of this complex were obtained at 25 °C upon slow evaporation of a CHCl3/MeOH solution. The molecular structure and its description are presented in the SI and Figure S87. In this structure, a bromine atom is in the apical position because of the replacement of the axial ligand of the starting compound by a bromine atom during the reaction with TMSBr. To the best of our knowledge, this is the first structural example on a gallium(III) meso-disubstituted porphyrin.
■
CONCLUSION In this contribution, the first examples of trivalent metal complexes of porphyrins bearing phosphonic acid and phosphonate ester groups at the meso position of the macrocycle are presented. The structural features of complexes In-1b and In-1c reveal the ability of indium(III) phosphorylated porphyrin to form five- and six-coordinate complexes, depending on the nature of the substituents located at the meso position of the macrocycle. The self-assembly of the monoester of meso-porphyrinylphosphonic acid Ga-2b into a dimer through the formation of strong bonds between oxygen atoms of the anions of meso-porphyrinylphosphonic acid monoester and gallium(III) cations of adjacent porphyrin molecules has been demonstrated. The first structural data for a gallium(III) meso-disubstituted porphyrin are also described. These new data on indium(III) and gallum(III) porphyrins should contribute to defining structural models for mimicking the native iron(III)-containing heme behavior. The synthesized compounds can also serve in biomedical imaging applications.
■
EXPERIMENTAL SECTION
General Procedures. Unless otherwise noted, all chemicals and starting materials were obtained commercially from Acros or Aldrich and used without further purification. Solvents were dried using standard procedures.63 Column chromatography purification was carried out on silica gel (MN Kieselgel 60, 63−200 μm, MachereyNagel). NMR spectra were acquired on Bruker Avance III 600 MHz and Bruker Avance II 300 MHz spectrometers and referenced to residual solvent protons (the Shared Facility Centers of the Institute of Physical Chemistry and Electrochemistry, RAS, and Institute of General and Inorganic Chemistry, RAS, respectively). UV−vis absorption spectra were obtained on a Helios Alpha spectrophotometer (Thermo Electron, USA) using a rectangular quartz cell (1− 10 mm). MALDI-TOF MS spectra were recorded on an Ultraflex mass spectrometer (Bruker Daltonics) in positive-ion mode unless otherwise stated with a dithranol matrix. Accurate mass measurements (HRMS) were made on a Thermo LTQ Orbitrap XL spectrometer equipped with an ESI source in positive-ion mode unless otherwise stated. Solutions in CHCl3/MeOH (1:1) were used for analysis. The measurements were made at the Pôle Chimie Moléculaire, the technological platform for chemical analysis and molecular synthesis (http://www.wpcm.fr), which relies on the Institute of the Molecular Chemistry of University of Burgundy and Welience, a Burgundy University private subsidiary. IR spectra were registered on FT-IR Nexus (Nicolet) and Bruker Vector 22 spectrophotometers. A universal micro-ATR sampling accessory (Pike) was used in order to obtain IR spectra of solid samples. X-ray Diffraction Studies. Single-crystal X-ray diffraction experiments were carried out on a Bruker SMART APEX II diffractometer with a CCD area detector (graphite monochromator, Mo Kα radiation, λ = 0.71073 Å, ω scans). Indexing was performed using APEX2.64 The intensities were corrected for absorption using SADABS.65 The structures were solved by direct methods and refined on F2 by full-matrix least-squares techniques with anisotropic displacement parameters for all non-hydrogen atoms. All hydrogen atoms in the complexes were placed geometrically and included in the I
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
General Procedure for the Preparation of [10-(Diethoxyphosphoryl)-5,15-diarylporphyrinato(2−)](chloro)indium(III) (In-1a−In1c). A 3.4 mM solution of the corresponding free base porphyrin 2H-1, indium(III) chloride (3 equiv), and sodium acetate (30 equiv) was refluxed in acetic acid for 20 min. During the heating, the color of the reaction mixture became magenta red. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was dissolved in CHCl3 and washed two times with H2O to remove the excess of indium and sodium salts. The organic layer was concentrated and purified by column chromatography on silica gel using a CHCl3/EtOH mixture as an eluent to afford In-1. [10-(Diethoxyphosphoryl)-5,15-diphenylporphyrinato(2−)](chloro)indium(III) (In-1a). The complex was prepared from 2H-1a (0.027 g, 0.045 mmol). The reaction mixture was chromatographed using a CHCl3/EtOH (70:30, v/v) mixture as an eluent to give In-1a as a violet crystalline powder in 98% yield (0.033 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.45 (s, 1H, Hmeso), 10.33 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 9.41 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.98 (d, 3 JH,H = 5.0 Hz, 2H, Hβ), 8.95 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.04 (bs, 4H, o-Ph), 7.65 (m, 6H, m+p-Ph), 4.39−4.24 (m, 2H, CH2O), 4.14−4.01 (m, 2H, CH2O), 1.15 (t, 3JH,H = 7.1 Hz, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 22.8. MS (MALDI-TOF). Calcd for C36H29ClInN4O3P ([M]+): m/z 746.1. Found: 746.0. Calcd for C36H29InN4O3P ([M − Cl]+): m/z 711.1. Found: m/z 711.0. HRMS (ESI). Calcd for C36H29InN4O3P ([M − Cl]+): m/z 711.10106. Found: m/z 711.10113. UV−vis [CHCl3; λmax, nm (log ε)]: 420 (5.38), 554 (4.28), 588 (4.11). IR (neat, cm−1): νmax 2958 (w), 2928 (w), 2857 (w), 1597 (w), 1575 (w), 1540 (w), 1516 (w), 1456 (w), 1441 (w), 1416 (w), 1386 (w), 1356 (w), 1286 (m), 1271 (m), 1249 (m, PO), 1215 (m), 1158 (w), 1121 (w), 1089 (w), 1067 (m), 1041 (m), 1007 (s, P−O), 960 (m, P−O), 889 (m), 875 (m), 800 (m), 781 (m), 749 (s), 730 (m), 715 (m), 700 (m), 668 (m), 654 (m), 619 (w), 577 (s), 568 (m), 568 (m), 557 (m). [10-(Diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato(2−)](chloro)indium(III) (In-1b). The complex was prepared from 2H-1b (0.030 g, 0.048 mmol). The reaction mixture was chromatographed using a CHCl3/EtOH (70:30, v/v) mixture as an eluent to give In-1b as a violet crystalline powder in 94% yield (0.035 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.41 (s, 1H, Hmeso), 10.31(d, 3JH,H = 5.0 Hz, 2H, Hβ), 9.38 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 9.00 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 8.96 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 7.92 (bd, 2H, o-Ph), 7.43 (d, 3JH,H = 8.0 Hz, 2H, m-Ph), 4.39−4.26 (m, 2H, CH2O), 4.13−4.00 (m, 2H, CH2O), 2.55 (s, 6H, CH3), 1.15 (t, 3JH,H = 7.1 Hz, 6H, CH3). 31P NMR (600 MHz, CDCl3, 25 °C): δP 23.1. MS (MALDI-TOF). Calcd.for C38H33ClInN4O3P ([M]+): m/z 774.1. Found: m/z 773.5. Calcd for C38H33InN4O3P ([M − Cl]+): m/z 739.1. Found: m/z 738.6. HRMS (ESI). Calcd for C38H33InN4O3P ([M − Cl]+): m/z 739.13236. Found: m/z 739.13298. UV−vis [CHCl3; λmax, nm (log ε)]: 420 (5.46), 554 (4.17), 586 (3.88). IR (neat, cm−1): νmax 2975 (w), 2883 (w), 2854 (w), 1516 (w), 1455 (w), 1415 (w), 1381 (w), 1356 (w), 1311 (w), 1252 (m, PO), 1211 (m), 1180 (m), 1157 (m), 1097 (m), 1064 (m), 1043 (m), 1007 (s, P−O), 959 (s, P−O), 890 (s), 876 (m), 858 (m), 876 (m), 868 (m), 847 (m), 785 (s), 737 (m), 718 (m), 705 (m), 642 (w), 595 (m), 587 (m), 576 (m), 556 (m). [10-(Diethoxyphosphoryl)-5,15-bis{4-(methoxycarbonyl)phenyl}porphyrinato(2−)](chloro)indium(III) (In-1c). The complex was prepared from 2H-1c (0.021 g, 0.029 mmol). The reaction mixture was chromatographed using a CHCl3/EtOH (90:10, v/v) mixture as an eluent to give In-1c as a violet crystalline powder in 91% yield (0.023 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.49 (s, 1H, Hmeso), 10.39 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 9.45 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.96 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 8.93 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.34 and 8.19 (AB system, 8H, m-Ph and o-Ph, respectively), 4.39−4.33 (m, 2H, CH2O), 4.14−4.07 (m, 2H, CH2O), 3.98 (s, 6H, CO2CH3), 1.18 (t, 3JH,H = 7.1 Hz, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 22.4. MS (MALDITOF). Calcd for C40H33ClInN4O7P ([M]+): m/z 862.1. Found: m/z 862.1. Calcd for C40H33InN4O7P ([M − Cl]+): m/z 827.1. Found: m/ z 827.1. HRMS (ESI). Calcd for C40H33InN4O7P ([M − Cl]+): m/z
was refluxed in acetic acid for 20 min. During the heating, the color of the reaction mixture became magenta red. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was dissolved in CHCl3 and washed two times with H2O to remove the excess of gallium and sodium salts. The organic layer was concentrated and purified by column chromatography on silica gel using a CHCl3/ethanol (EtOH) mixture as an eluent. Combined colored fractions were evaporated under reduced pressure to afford Ga-1. [10-(Diethoxyphosphoryl)-5,15-diphenylporphyrinato(2−)](acetato)gallium(III) (Ga-1a). The complex was prepared from 2H-1a (0.027 g, 0.045 mmol). The resulting crude solid was chromatographed using a CHCl3/EtOH (70:30, v/v) mixture as an eluent to give Ga-1a as a violet crystalline powder in 92% yield (0.030 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.35 (s, 1H, Hmeso), 10.31 (d, 3JH,H = 5.1 Hz, 2H, Hβ), 9.37 (d, 3JH,H = 4.7 Hz, 2H, Hβ), 9.00 (d, 3JH,H = 5.1 Hz, 2H, Hβ), 8.94 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 7.98 (d, 3JH,H = 6.2 Hz, 4H, o-Ph), 7.63 (m, 6H, m+p-Ph), 4.33−4.27 (m, 2H, CH2O), 4.09−4.02 (m, 2H, CH2O), 1.16 (t, 3JH,H = 7.1 Hz, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 22.1. HRMS (ESI). Calcd for C36H29GaN4O3P ([M − OAc]+): m/z 665.12276. Found: m/z 665.12457. UV−vis [CHCl3; λmax, nm (log ε)]: 414 (5.26), 546 (4.15), 584 (3.92). IR (neat, cm−1): νmax 2974 (w), 2923 (w), 2854 (w), 1598 (m), 1532 (w), 1485 (w), 1440 (w, COO), 1389 (w), 1367 (w), 1322 (w), 1291 (w), 1250 (m, PO), 1206 (m, PO), 1148 (m), 1069 (m), 1042 (m), 1007 (s, P−O), 957 (m, P−O), 890 (m), 874 (m), 786 (s), 750 (s), 727 (s), 714 (m), 700 (s), 656 (m), 603 (m), 581 (s), 569 (s), 561 (s), 554 (s). [10-(Diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato(2−)](acetato)gallium(III) (Ga-1b). The complex was prepared from 2H-1b (0.150 g, 0.239 mmol). The resulting crude solid was chromatographed using a CHCl3/EtOH (90:10, v/v) mixture as an eluent to give Ga-1b as a violet crystalline powder in 96% yield (0.170 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.31 (s, 1H, Hmeso), 10.30 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 9.35 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 9.03 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 8.97 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 7.87 (d, 3JH,H = 7.4 Hz, 4H, o-Ph), 7.43 (d, 3JH,H = 7.4 Hz, 4H, m-Ph), 4.32−4.26 (m, 2H, CH2O), 4.08−4.01 (m, 2H, CH2O), 2.53 (s, 6H, CH3), 1.17 (t, 3JH,H = 7.1 Hz, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 22.3. HRMS (ESI). Calcd for C38H33GaN4O3P ([M − OAc]+): m/z 693.15406. Found: m/z 693.15454. UV−vis [CHCl3/MeOH, 95:5, v/v; λmax, nm (log ε)]: 417 (5.45), 547 (4.20), 584 (3.91). IR (neat): νmax (cm−1) 2980 (w), 2925 (w), 2885 (w), 1610 (w, COO), 1533 (w), 1490 (w), 1437 (w, COO), 1388 (w), 1364 (w), 1323 (w), 1294 (w), 1248 (m, PO), 1209 (m, PO), 1182 (m), 1159 (m), 1092 (m), 1067 (m), 1041 (m), 1002 (s, P−O), 955 (s, P−O), 892 (s), 876 (m), 849 (m), 795 (s), 735 (m), 713 (m), 697 (m), 668 (w), 597 (s), 568 (s), 557 (m). [10-(Diethoxyphosphoryl)-5,15-bis{4-(methoxycarbonyl)phenyl}porphyrinato(2−)](acetato)gallium(III) (Ga-1c). The complex was prepared from 2H-1c (0.024 g, 0.034 mmol). The resulting crude solid was chromatographed using a CHCl3/EtOH (70:30, v/v) mixture as an eluent to give Ga-1c as a violet crystalline powder in 88% yield (0.025 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.46 (s, 1H, Hmeso), 10.38 (d, 3JH,H = 5.1 Hz, 2H, Hβ), 9.45 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.98 (d, 3JH,H = 5.1 Hz, 2H, Hβ), 8.94 (d, 3JH,H = 4.7 Hz, 2H, Hβ), 8.31 and 8.11 (AB system, JAB = 8.2 Hz, 8H, m-Ph and oPh, respectively), 4.41−4.26 (m, 2H, CH2O), 4.12−4.04 (m, 2H, CH2O), 3.95 (s, 6H, CO2CH3), 1.18 (t, 3JH,H = 7.1 Hz, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 21.6. HRMS (ESI). Calcd for C40H33GaN4O7P ([M − OAc]+): m/z 781.13372. Found: m/z 781.13603. UV−vis [CHCl3; λmax, nm (log ε)]: 416 (5.42), 548 (4.13), 584 (3.89). IR (neat, cm−1): νmax 2984 (w), 2951 (w), 2903 (w), 1720 (s, CO), 1607 (m, COO), 1557 (w), 1538 (w), 1532 (w), 1435 (m, COO), 1393 (w), 1367 (w), 1309 (w), 1273 (s), 1251 (m, PO), 1208 (m, PO), 1190 (m), 178 (m), 1160 (m), 1111 (s), 1099 (s), 1070 (m), 1041 (m), 1005 (s, P−O), 960 (s, P−O), 895 (s), 866 (s), 821 (m), 798 (s), 761 (s), 733 (s), 715 (m), 705 (m), 667 (m), 636 (w), 582 (s), 571 (w), 556 (m). J
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry 827.11202. Found: m/z 827.11306. UV−vis [CHCl3; λmax, nm (log ε)]: 420 (5.39), 552 (4.08), 588 (3.71). IR (neat, cm−1): νmax 2982 (w), 2947 (w), 2923 (w), 2848 (w), 1721 (s, CO), 1607 (m), 1455 (w), 1435 (m), 1309 (m), 1277 (s), 1247 (m, PO), 1215 (w), 1178 (w), 1160 (w), 1112 (m), 1100 (m), 1069 (m), 1042 (m), 1009 (s, P− O), 965 (m, P−O), 894 (w), 867 (m), 801 (m), 765 (m), 734 (w), 581 (m). General Procedure for the Preparation of [10-(Ethoxyhydroxyphosphoryl)-5,15-diarylporphyrinato(2−)](hydroxo)gallium/ indium(III) (Ga-2a, Ga-2b, In-2a, and In-2b). To a solution of Ga-1 or In-1 (1 equiv) in a mixture of THF and MeOH (2:1, v/v, 1.2 mmol/L) was added a solution of NaOH (150 equiv) in H2O (0.5 M). The resulting mixture was refluxed for 1 day. Then the solution was cooled to room temperature, neutralized with 0.5 M hydrochloric acid until product precipitated, which was filtered, washed two times with H2O, dissolved in CHCl3, and subjected to column chromatography on silica gel to afford Ga-2a, Ga-2b, In-2a, or In-2b. [10-(Ethoxyhydroxyphosphoryl)-5,15-diphenylporphyrinato(2−)](hydroxo)gallium(III) (Ga-2a). The complex was prepared by the reaction of a NaOH (0.114 g, 2.85 mmol) solution in H2O with a solution of Ga-1a (0.013 g, 0.018 mmol) in 15 mL of a THF/MeOH mixture in a manner similar to that described above. The reaction mixture was chromatographed using a CHCl3/MeOH (60:40, v/v) mixture as an eluent to afford Ga-2a as a brown-red crystalline powder in 90% yield (0.011 g). The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.61 (d, 3JH,H = 5.1 Hz, 2H, Hβ), 10.27 (s, 1H, Hmeso), 9.36 (d, 3JH,H = 4.7 Hz, 2H, Hβ), 8.93 (d, 3JH,H = 4.8 Hz, 2H, Hβ), 8.92 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 7.99 (d, 3JH,H = 6.0 Hz, 4H, o-Ph), 7.62 (m, 6H, m+p-Ph), 3.88−3.74 (m, 2H, CH2O), 0.94 (t, 3 JH,H = 7.0 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 13.6. HRMS (ESI). Calcd for C34H25GaN4O3P ([M − OH]+): m/z 637.09146. Found: m/z 637.09292. UV−vis [CHCl3/MeOH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 412 (5.53), 546 (4.22), 580 (3.68). IR (neat, cm−1): νmax 3384 (br w, OH), 2922 (w), 2849 (w), 1651 (w), 1557 (w), 1485 (m), 1440 (w), 1389 (w), 1371 (w), 1335 (w), 1324 (w), 1268 (w, PO), 1208 (w, PO), 1145 (s), 1103 (w), 1076 (m), 1058 (m), 1022 (m), 1010 (s, P−O), 996 (m, P−O), 936 (m, P−O), 887 (m), 873 (w), 846 (m), 783 (s), 741 (s), 727 (m), 697 (s), 656 (m), 601 (s), 560 (m). [10-(Ethoxyhydroxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato(2−)](hydroxo)gallium(III) (Ga-2b). The complex was prepared by the reaction of a NaOH (0.165 g, 4.11 mmol) solution in H2O with a solution of Ga-1b (0.019 g, 0.026 mmol) in 22.5 mL of a THF/ MeOH mixture in a manner similar to that described above. The reaction mixture was chromatographed using a CHCl3/MeOH (70:30, v/v) mixture as an eluent to afford Ga-2b as a brown-red crystalline powder in 76% yield (0.014 g). The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.60 (d, 3 JH,H = 5.1 Hz, 2H, Hβ), 10.26 (s, 1H, Hmeso), 9.35 (d, 3JH,H = 4.7 Hz, 2H, Hβ), 8.97 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 8.95 (d, 3JH,H = 5.5 Hz, 2H, Hβ), 7.86 (d, 3JH,H = 7.9 Hz, 4H, o-Ph), 7.41 (d, 3JH,H = 7.8 Hz, 4H, mPh), 3.95−3.81 (m, 2H, CH2O), 2.54 (s, 6H, CH3), 0.98 (t, 3JH,H = 7.1 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 13.9. HRMS (ESI). Calcd for C36H29GaN4O3P ([M − OH]+): m/z 665.12276. Found: m/z 665.12325. UV−vis spectra [CHCl3/MeOH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 414 (5.36), 546 (4.10), 582 (3.65). IR (neat, cm−1): νmax 3305 (br w, OH), 2917 (w), 2854 (w), 1601 (w), 1533 (w), 1515 (w), 1488 (w), 1437 (w), 1388 (w), 1357 (w), 1335 (w), 1290 (w), 1265 (w, PO), 1206 (w, PO), 1182 (w), 1145 (s), 1104 (m), 1072 (m), 1057 (m),
1021 (w), 1006 (s, P−O), 937 (m, P−O), 887 (m), 876 (w), 848 (m), 821 (w), 795 (s), 784 (s), 734 (m), 703 (m), 696 (m), 668 (m), 611 (s), 576 (m), 568 (m), 562 (m), 556 (m). [10-(Ethoxyhydroxyphosphoryl)-5,15-diphenylporphyrinato(2−)](hydroxo)indium(III) (In-2a). The complex was prepared by the reaction of a NaOH (0.088 g, 2.21 mmol) solution in H2O with a solution of In-1a (0.011 g, 0.015 mmol) in 11.7 mL of a THF/MeOH mixture in a manner similar to that described above. The reaction mixture was chromatographed using a CHCl3/MeOH (60:40, v/v) mixture as an eluent to afford In-2a as a brown-red crystalline powder in 66% yield (0.007 g). The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.65 (bs, 2H, Hβ), 10.37 (s, 1H, Hmeso), 9.40 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.96 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.92 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 8.05 (bs, 3JH,H = 6.0 Hz, 4H, o-Ph), 7.65 (m, 6H, m+p-Ph), 3.92−3.70 (m, 2H, CH2O), 0.92 (t, 3JH,H = 7.2 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 14.3. HRMS (ESI). Calcd for C34H25InN4O3P ([M − OH]+): m/z 683.06976. Found: m/z 683.06931. UV−vis [CHCl3/MeOH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 416 (5.36), 552 (4.16), 586 (3.71). IR (neat, cm−1): νmax 3396 (br w, OH), 2922 (w), 2851 (w), 1594 (w), 1267 (w, PO), 1219 (w), 1205 (w, P O), 1165 (s), 1078 (m), 1060 (m), 1015 (s, P−O), 938 (m, P−O), 886 (m), 876 (w), 846 (m), 779 (s), 744 (m), 725 (m), 696 (s), 668 (m), 654 (m), 613 (w), 600 (s), 590 (m), 575 (m), 569 (w), 564 (m), 560 (m), 556 (m). [10-(Ethoxyhydroxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato(2−)](hydroxo)indium (III). In-2b was prepared by the reaction of a NaOH (0.108 g, 2.70 mmol) solution in H2O with a solution of In-1b (0.014 g, 0.018 mmol) in 15 mL of a THF/MeOH mixture in a manner similar to that described above. The reaction mixture was chromatographed using a CHCl3/MeOH (70:30, v/v) mixture as an eluent to afford In-2b as a brown-red crystalline powder in 90% yield (0.012 g). The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.67 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 10.37 (s, 1H, Hmeso), 9.40 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 9.00 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.97 (d, 3 JH,H = 5.0 Hz, 2H, Hβ), 7.93 (d, 3JH,H = 7.8 Hz, 4H, o-Ph), 7.45 (d, 3 JH,H = 7.8 Hz, 4H, m-Ph), 3.97−3.77 (m, 2H, CH2O), 2.58 (s, 6H, CH3), 0.94 (t, 3JH,H = 7.1 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 14.7. HRMS (ESI). Calcd for C36H29InN4O3P ([M − OH]+): m/z 711.10108. Found: m/z 711.09983. UV−vis [CHCl3/ MeOH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 420 (5.13), 554 (3.92), 592 (3.57). IR (neat, cm−1): νmax 3295 (br w, OH), 2953 (w), 2919 (m), 2850 (m), 2523 (br w), 1517 (w), 1507 (w), 1457 (w), 1419 (w), 1387 (w), 1356 (w), 1287 (w), 1259 (w, PO), 1211 (w, PO), 1168 (s), 1105 (m), 1079 (m), 1066 (m), 1064 (m), 1030 (m), 1014 (s, P−O), 942 (m, P−O), 888 (m), 848 (m), 816 (w), 794 (m), 785 (m), 737 (m), 718 (m), 694 (m), 661 (w), 608 (s), 587 (m), 574 (m), 558 (m). General Procedure for the Preparation of [10-(Ethoxyhydroxyphosphoryl)-5,15-bis{4-carboxyphenyl}porphyrinato(2−)](hydroxo)gallium/indium(III) (Ga-3c and In-3c). To a solution of Ga-1c or In-1c (1 equiv) in a mixture of THF and MeOH (2:1, v/v, 1.2 mmol/L) was added a solution of NaOH (150 equiv) in H2O (0.5 M). The resulting mixture was refluxed for 1 day. Then the solution was cooled to room temperature and neutralized with 0.5 M hydrochloric acid until the product precipitated, which was filtered and washed two times with H2O and two times with acetone. The precipitate was collected and dried under reduced pressure at 25 °C. The insolubility of these complexes in organic solvents has prevented the purification of reaction products by column chromatography. K
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry [10-(Ethoxyhydroxyphosphoryl)-5,15-bis{4-carboxyphenyl}porphyrinato(2−)](hydroxo)gallium(III) (Ga-3c). The complex was prepared by the reaction of a NaOH (0.090 g, 2.25 mmol) solution in H2O with a solution of Ga-1c (0.012 g, 0.014 mmol) in 11.7 mL of a THF/MeOH mixture in a manner similar to that described above as a brown-red crystalline powder. The yield is 86% (0.009 g). The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1 H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.57 (bs, 2H, Hβ), 10.20 (s, 1H, Hmeso), 9.29 (bs, 2H, Hβ), 8.88 (d, 3JH,H = 4.3 Hz, 2H, Hβ), 8.87 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 8.17 and 7.97 (AB system, JAB = 7.8 Hz, 8H, m-Ph and o-Ph, respectively), 3.83−3.78 (m, 2H, CH2O), 0.93 (t, 3JH,H = 7.0 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 14.1. 1H NMR (600 MHz, D2O + 1 drop of a saturated solution of NaOH in D2O, 80 °C): δH 11.33 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 9.78 (d, 3JH,H = 5.1 Hz, 2H, Hβ), 9.62 (s, 1H, Hmeso), 9.21 (bs, 4H, Hβ), 8.93 and 8.67 (AB system, JAB = 7.9 Hz, 8H, m-Ph and o-Ph, respectively), 4.71−4.66 (m, 2H, CH2O), 1.84 (t, 3JH,H = 7.1 Hz, 3H, CH3). MS (MALDI-TOF). Calcd for C72H48Ga2N8O14P2 ([{M − OH − H}2 + H]+): m/z 1449.14. Found: 1450.80. HRMS (ESI). Calcd for C36H25GaN4O7P ([M − OH]+): m/z 725.07112. Found: m/z 725.07285. UV−vis [CHCl3/MeOH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 416 (5.57), 548 (4.28), 584 (3.78). IR (neat, cm−1): νmax 2981 (w), 1695 (s, C O), 1606 (s, CO), 1552 (m), 1505 (w), 1402 (w), 1310 (w), 1267 (m, PO), 1220 (m), 1149 (m), 1112 (m), 1070 (m), 1006 (s, P−O), 948 (w), 892 (m), 865 (m), 827 (w), 788 (s), 763 (s), 732 (s), 707 (m), 668 (m), 636 (m), 600 (s), 581 (s), 556 (s). Anal. Calcd for C36H24N4O8PGaNa2: C, 53.24; H, 2.98; N, 6.90. Found: C, 52.89; H, 4.12; N, 7.48. [10-(Ethoxyhydroxyphosphoryl)-5,15-bis{4-carboxyphenyl}porphyrinato(2−)](hydroxo)indium(III) (In-3c). The complex was prepared by reacting a NaOH (0.070 g, 1.74 mmol) solution in H2O with a solution of In-1c (0.010 g, 0.012 mmol) in 9 mL of a THF/ MeOH mixture in a manner similar to that described above as a brown-red crystalline powder. The yield is 75% (0.007 g). The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1 H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.61 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 10.38 (s, 1H, Hmeso), 9.40 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.94 (d, 3JH,H = 4.3 Hz, 2H, Hβ), 8.88 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 8.20 and 8.04 (AB system, JAB = 7.8 Hz, 8H, m-Ph and o-Ph, respectively), 3.84−3.78 (m, 2H, CH2O), 0.88 (t, 3JH,H = 7.0 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 14.5. 1H NMR (600 MHz, D2O + 1 drop of a saturated solution of NaOH in D2O, 90 °C): δH 11.31 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 9.79 (s, 1H, Hmeso), 9.71 (d, 3JH,H = 5.0 Hz, 2H, Hβ), 9.21 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 9.05 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 8.92 and 8.57 (AB system, JAB = 7.9 Hz, 8H, m-Ph and o-Ph, respectively), 4.70−4.61 (m, 2H, CH2O), 1.80 (t, 3JH,H = 7.1 Hz, 3H, CH3). MS (MALDI-TOF). Calcd for C72H48In2N8O14P2 ([{M − OH − H}2]+): m/z 1540.08. Found: m/z 1540.65. UV−vis [CHCl3/ MeOH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 420 (5.63), 554 (4.38), 594 (3.78). IR (neat, cm−1): νmax 3002 (w), 1696 (s, CO), 1606 (s, CO), 1566 (m), 1508 (m) 1402 (m), 1310 (m), 1260 (m, PO), 1206 (m), 1160 (s), 1112 (m), 1070 (m), 1011 (s, P−O), 942 (w), 892 (m), 865 (m), 822 (m), 785 (s), 762 (s), 732 (s), 707 (m), 668 (m), 636 (m), 600 (s), 581 (s), 556 (s). Anal. Calcd for C36H24N4O8PInNa2·6H2O: C, 45.25; H, 3.80; N, 5.86. Found: C, 44.83; H, 3.61; N, 6.35. General Procedure for the Preparation of Free Base Monoester of meso-Porphyrinylphosphonic Acids (2H-2a, 2H-2b, and 2H-3c). To a solution of the free base porphyrin 2H-1 (1 equiv) in a mixture of
THF and MeOH (2:1, v/v, 1.2 mmol/L) was added a solution of NaOH (150 equiv) in H2O (0.5 M). The resulting mixture was refluxed for 1 day. Then the solution was cooled to room temperature and neutralized with 0.5 M hydrochloric acid. When pH = 7, the color of the reaction solution became blue-green. Acid was added to pH = 2. After that, the reaction solution of 2H-2a and 2H-2b was extracted with CHCl3 (3 × 100 mL). The organic layer was washed with H2O (2 × 50 mL). At the same time, the color of the solution became redviolet. Then, it was concentrated under reduced pressure and purified on silica gel using a CHCl3/MeOH mixture as an eluent. For 2H-1c, the 0.5 M hydrochloric acid solution was added until the product precipitated, which was filtered, washed two times with H2O, collected, and dried under reduced pressure at 25 °C. The simultaneous hydrolysis of methoxycarbonyl to carboxy groups was observed. The insolubility of this compound in organic solvents has prevented the purification of the reaction product by column chromatography. 10-(Ethoxyhydroxyphosphoryl)-5,15-diphenylporphyrin (2H-2a). The complex was prepared from 2H-1a (0.0096 g, 0.016 mmol). The resulting crude solid was chromatographed using a CHCl3/EtOH (95:5, v/v) mixture as an eluent to give 2H-2a as a violet crystalline powder in 98% yield (0.0089 g).1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.26 (bs, 2H, Hβ), 10.09 (s, 1H, Hmeso), 9.11 (d, 3 JH,H = 4.2 Hz, 2H, Hβ), 8.64 (d, 3JH,H = 4.0 Hz, 2H, Hβ), 8.55 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 7.84 (d, 3JH,H = 6.8 Hz, 4H, o-Ph), 7.48 (m, 6H, m +p-Ph), 3.75−3.58 (m, 2H, CH2O), 0.75 (t, 3JH,H = 7.0 Hz, 3H, CH3). 31 P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 14.3. HRMS (ESI). Calcd for C34H28N4O3P ([M + H]+): m/z 571.18965. Found: m/z 571.18935. Calcd for C34H27NaN4O3P ([M + Na]+): m/z 593.17130. Found: m/z 593.17081. UV−vis [CHCl3/MeOH, 50:50, v/v; λmax, nm (log ε)]: 412 (5.18), 510 (3.98), 542 (3.78), 582 (3.83), 634 (3.61). IR (neat, cm−1): νmax 3315 (br w, OH), 2956 (m), 2921 (m), 2851 (m), 2355 (br m, OH), 1731 (w), 1589 (w), 1482 (w), 1457 (m), 1436 (m), 1311 (w), 1271 (w, PO), 1246 (w, PO), 1219 (w), 1201 (w, PO), 1183 (w), 1159 (m), 1112 (m), 1065 (s), 1011 (s, P−O), 972 (s, P−O), 958 (s, P−O), 891 (m), 864 (m), 829 (w), 760 (s), 736 (s), 714 (s), 691 (s), 622 (m), 610 (m). 10-(Ethoxyhydroxyphosphoryl)-5,15-bis(p-tolyl)porphyrin (2H2b). The complex was prepared from 2H-1b (0.010 g, 0.016 mmol). The resulting crude solid was chromatographed using a CHCl3/EtOH (95:5, v/v) mixture as an eluent to give 2H-2b as a violet crystalline powder in 98% yield (0.0094 g). 1H NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, 25 °C): δH 10.30 (bs, 2H, Hβ), 10.03 (s, 1H, Hmeso), 9.09 (bs, 2H, Hβ), 8.65 (bs, 2H, Hβ), 8.58 (bs, 2H, Hβ), 7.67 (d, 3JH,H = 6.8 Hz, 4H, o-Ph), 7.17 (d, 3JH,H = 6.9 Hz, 4H, m-Ph), 3.68−3.58 (m, 2H, CH2O), 2.39 (s, 6H, CH3), 0.72 (t, 3JH,H = 7.1 Hz, 3H, CH3). 31 P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δP 14.9. HRMS (ESI). Calcd for C36H32N4O3P ([M + H]+): m/z 599.22065. Found: m/z 599.21996. UV−vis [CHCl3/MeOH, 95:5, v/v; λmax, nm (log ε)]: 415 (5.45), 511 (4.32), 542 (3.94), 585 (3.99), 637 (3.34). IR (neat, cm−1): νmax 3312 (br w, OH), 2970 (w), 2924 (w), 2858 (w), 2365 (br m, OH), 1543 (w), 1460 (w), 1402 (w), 1236 (w, P O), 1220 (w), 1211 (m, PO), 1193 (m), 1180 (w), 1142 (w), 1015 (P−O), 972 (w, P−O), 955 (s, P−O), 882 (m), 869 (m), 853 (m), 838 (m), 788 (s), 780 (s), 756 (m), 739 (s), 726 (s), 692 (m), 668 (w). 10-(Ethoxyhydroxyphosphoryl)-5,15-bis(4-carboxyphenyl)porphyrin (2H-3c). The complex was prepared from 2H-1c (0.014 g, 0.016 mmol). The resulting crude solid was washed two times with H2O, collected, and dried under reduced pressure at 25 °C to give 2H3c as a violet crystalline powder in 96% yield (0.0105 g). The target complex was almost insoluble in organic solvents and, thus, characterized with NMR spectroscopy as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O. 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.37 (bs, 2H, Hβ), 10.01 (s, 1H, Hmeso), 9.08 (bs, 2H, Hβ), 8.64 (bs, 4H, Hβ), 8.14 and 7.96 (AB system, JAB = 7.0 Hz, 8H, m-Ph and o-Ph, respectively), 3.66−3.53 (m, 2H, CH2O), 0.80 (t, 3JH,H = 7.1 Hz, 3H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 15.4. HRMS (ESI). Calcd for L
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry C36H28N4O7P ([M + H]+): m/z 659.1696. Found: m/z 659.1690. UV−vis [CHCl3/MeOH, 50:50, v/v; λmax, nm (log ε)]: 414 (5.44), 510 (4.28), 542 (3.78), 584 (3.92), 636 (3.60). IR (neat, cm−1): νmax 3315 (br w, OH), 2958 (w), 2920 (w), 2849 (w), 2477 (br w, OH),1682 (s, CO), 1605 (m), 1557 (w), 1538 (w), 1505 (w), 1422 (w), 1418 (w), 1403 (w), 1397 (w), 1397 (w), 1386 (w), 1312 (w), 1277 (m, PO), 1241 (m, PO), 1196 (m), 1176 (m), 1171 (m), 1117 (m), 1102 (m), 1065 (s), 1040 (s), 1017 (m, P−O), 1000 (w, P−O), 975 (m, P−O), 957 (m, P−O), 941 (m), 883 (w), 864 (s), 845 (m), 785 (s), 763 (s), 739 (s), 723 (m), 707 (m), 688 (w), 674 (w), 667 (m), 585 (w), 565 (s), 556 (m). General Procedure for the Preparation of Gallium(III) and Indium(III) Complexes with meso-Porphyrinylphosphonic Acids. A round-bottom flask was charged with the corresponding compound Ga-1 or In-1 (1 equiv), and the evacuation/inert gas refill cycle was repeated three times. Anhydrous CH2Cl2, triethylamine (15 equiv), and bromotrimethylsilane (50 equiv) were added by syringe, and the reaction mixture was stirred for 18 h at room temperature. The volatiles were distilled under reduced pressure, and the reaction vessel was refilled with argon. MeOH (2 mL) was added, and the solution was stirred for 1 h at room temperature. Evaporation of the volatiles afforded Ga-4 and In-4 as a violet crystalline powder in quantitative yield (according to NMR) together with triethylammonium bromide as a byproduct. The insolubility of the reaction products in organic solvents has prevented their purification by column chromatography. [(5,15-Diphenylporphyrin-10-yl)phosphonic acid](bromo)gallium(III) Bis(triethylammonium) Salt (Ga-4a). The complex was prepared from Ga-1a (0.017 g, 0.0234 mmol) in 2.7 mL of CH2Cl2. The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.75 (d, 3JH,H = 4.8 Hz, 2H, Hβ), 10.19 (s, 1H, Hmeso), 9.32 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 8.89 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 8.82 (d, 3 JH,H = 4.8 Hz, 2H, Hβ), 7.94 (d, 3JH,H = 6.9 Hz, 4H, o-Ph), 7.59 (m, 6H, m+p-Ph). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 12.0. MS (MALDI-TOF). Calcd for C64H41Ga2N8O6P2 ([{M − Br − H}2 + H]+): m/z 1217.1. Found: m/z 1217.2. UV−vis [CHCl3/CH3OH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 412 (5.42), 546 (4.20), 584 (3.71). IR (neat, cm−1): νmax 3382 (br w, OH), 2975 (m), 2933 (m), 2877 (w), 2801 (w), 2736 (m), 2673 (s), 2598 (w), 2490 (m), 1557 (w), 1538 (w), 1504 (w), 1475 (m), 1470 (m), 1463 (w), 1455 (w), 1438 (w), 1435 (m), 1397 (m), 1383 (w), 1170 (s, PO), 1155 (m), 1067 (m), 1034 (s), 1004 (m, P−O), 928 (m, P−O), 848 (m), 803 (m), 789 (m), 748 (m), 729 (m), 699 (m), 667 (w), 654 (w), 581 (m), 577 (m), 555 (m), 265 (m, Ga−Br). Anal. Calcd for C44H51BrN6O3PGa·17Et3NHBr: C, 44.17; H, 8.20; N, 8.11. Found: C, 44.14; H, 7.44; N, 7.90. [(5,15-Bis(p-tolyl)porphyrin-10-yl)phosphonic acid](bromo)gallium(III) Bis(triethylammonium) Salt (Ga-4b). The complex was prepared from Ga-1b (0.017 g, 0.0226 0.0230 mmol) in 2.7 mL of CH2Cl2. The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.72 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 10.18 (s, 1H, Hmeso), 9.31 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 8.92 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 8.84 (d, 3 JH,H = 4.5 Hz, 2H, Hβ), 7.81 (d, 3JH,H = 7.7 Hz, 4H, o-Ph), 7.37 (d, 3 JH,H = 7.6 Hz, 4H, m-Ph), 2.51 (s, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D 2 O, 25 °C): δ P 12.0. MS (MALDI-TOF). Calcd for C68H49Ga2N8O6P2 ([{M − Br − H}2 + H]+): m/z 1273.2. Found: m/z 1273.4. UV−vis [CHCl3/CH3OH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 414 (5.54), 548 (4.30), 584 (3.68). IR (neat, cm−1): νmax 3387 (br w, OH), 2974 (m), 2933 (m), 2877 (w), 2801 (w), 2752 (m), 2736 (m), 2672 (s), 2599 (w), 2490 (m), 2165 (m), 1502 (w), 1470 (m), 1463 (w), 1397
(s), 1383 (m), 1185 (w), 1169 (s, PO), 1076 (m), 1067 (m), 1034 (s), 1004 (m, P−O), 932 (m, P−O), 847 (m), 803 (m), 785 (m), 734 (w), 667 (m), 598 (m), 573 (m). Anal. Calcd for C46H55BrN6O3PGa· 14Et3NHBr: C, 45.19; H, 8.14; N, 8.11. Found: C, 45.14; H, 7.09; N, 7.90. [(5,15-Bis{4-(methoxycarbonyl)phenyl}porphyrin-10-yl)phosphonic acid](bromo)gallium(III) Bis(triethylammonium) Salt (Ga-4c). The complex was prepared from Ga-1c (0.014 g, 0.0166 mmol) in 2 mL of CH2Cl2. The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.77 (d, 3 JH,H = 4.9 Hz, 2H, Hβ), 10.21 (s, 1H, Hmeso), 9.34 (d, 3JH,H = 4.6 Hz, 2H, Hβ), 8.83 (d, 3JH,H = 4.5 Hz, 2H, Hβ), 8.77 (d, 3JH,H = 4.9 Hz, 2H, Hβ), 8.24 and 8.06 (AB system, JAB = 8.0 Hz, 8H, m-Ph and o-Ph, respectively), 4.12 (s, 6H, CO2CH3). 31P NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 11.0. MS (MALDI-TOF). Calcd for C72H49Ga2N8O14P2 ([{M − Br − H}2 + H]+): m/z 1449.1. Found: m/z 1449.4. UV−vis [CHCl3/CH3OH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 414 (5.65), 548 (4.44), 586 (3.83). IR (neat, cm−1): νmax 2974 (w), 2933 (w), 2874 (w), 2755 (w), 2736 (w), 2675 (m), 2489 (w), 2165 (m), 1732 (s), 1722 (s, CO), 1716 (s, CO), 1699 (m), 1435 (m), 1396 (m), 1306 (w), 1276 (s, P O), 1171 (m, PO), 1157 (m), 1107 (m), 1097 (m), 1067 (m), 1035 (m), 1002 (s, P−O), 934 (s, P−O), 862 (m), 820 (w), 792 (m), 758 (m), 733 (m), 713 (w), 705 (w), 697 (w), 691 (w), 587 (s), 271 (m, Ga−Br). Anal. Calcd for C48H55BrN6O7PGa·14Et3NHBr: C, 44.75; H, 7.94; N, 7.91. Found: C, 44.52; H, 7.28; N, 7.74. [(5,15-Diphenylporphyrin-10-yl)phosphonic acid](bromo)indium(III) Bis(triethylammonium) Salt (In-4a). The complex was prepared from In-1a (0.0246 g, 0.0329 335 mmol) in 3.7 mL of CH2Cl2. The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.80 (d, 3JH,H = 4.8 Hz, 2H, Hβ), 10.28 (s, 1H, Hmeso), 9.36 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.92 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.83 (d, 3 JH,H = 4.8 Hz, 2H, Hβ), 8.01 (d, 3JH,H = 6.9 Hz, 4H, o-Ph), 7.62 (m, 6H, m+p-Ph). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δP 12.0. MS (MALDI-TOF). Calcd for C32H21BrInN4O3P ([M]+): m/z 734.0. Found: m/z 734.1. Calcd for C64H41In2N8O6P2 ([{M − Br − H}2 + H]+): 1309.1. Found: m/z 1309.4. UV−vis [CHCl3/CH3OH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 416 (5.11), 552 (3.95), 586 (3.61). IR (neat, cm−1): νmax 3365 (br w, OH), 2972 (m), 2931 (m), 2875 (w), 2738 (m), 2674 (s), 2489 (m), 2225 (m), 1475 (m), 1470 (m), 1463 (m), 1455 (w), 1446 (w), 1435 (m), 1397 (m), 1383 (w), 1361 (w), 1287 (m), 1270 (m, P O), 1170 (s, PO), 1120 (w), 1068 (m), 1035 (s), 1012 (s, P−O), 928 (m, P−O), 848 (m), 803 (s), 788 (m), 748 (m), 730 (w), 700 (m), 666 (w), 652 (w), 586 (m), 573 (s), 558 (m), 234 (m, In−Br). Anal. Calcd for C44H51BrN6O3PIn·15Et3NHBr: C, 44.05; H, 8.03; N, 8.05. Found: C, 44.07; H, 7.73; N, 6.95. [(5,15-Bis(p-tolyl)porphyrin-10-yl)phosphonic acid](bromo)indium(III) Bis(triethylammonium) Salt (In-4b). The complex was prepared from In-1b (0.019 g, 0.0245 mmol) in 2.7 mL of CH2Cl2. The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.79 (d, 3JH,H = 4.8 Hz, 2H, Hβ), 10.27 (s, 1H, Hmeso), 9.35 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.96 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.86 (d, 3 JH,H = 4.8 Hz, 2H, Hβ), 7.88 (d, 3JH,H = 7.7 Hz, 4H, o-Ph), 7.41 (d, 3 JH,H = 7.5 Hz, 4H, m-Ph), 2.54 (s, 6H, CH3). 31P NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in M
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
■
D2O in D2O, 25 °C): δP 12.5. MS (MALDI-TOF). Calcd for C34H25BrInN4O3P ([M]+): m/z 762.0. Found: m/z 762.2. Calcd for C68H49In2N8O6P2 ([{M − Br − H}2 + H]+): m/z 1365.1. Found: m/z 1365.5. HRMS (ESI). Calcd for C34H25InN4O3P ([M − Br]+): m/z 683.06976. Found: m/z 683.06969. UV−vis [CHCl3/CH3OH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O; λmax, nm (log ε)]: 420 (5.27), 554 (4.11), 592 (3.70). IR (neat, cm−1): νmax 3343 (br w, OH), 2975 (w), 2928 (m), 2754 (w), 2737 (w), 2675 (s), 2490 (m), 1505 (w), 1475 (m), 1470 (m), 1435 (m), 1397 (m), 1383 (w), 1289 (w, PO), 1204 (m, PO), 1183 (m), 1170 (m), 1102 (w), 1067 (w), 1035 (s), 1014 (s, P−O), 927 (w, P−O), 896 (m), 848 (m), 786 (s), 733 (m), 706 (m), 690 (m), 667 (m), 635 (w), 600 (s), 590 (m), 571 (s), 554 (m), 551 (s), 234 (m, In−Br). Anal. Calcd for C46H55BrN6O3PIn·13Et3NHBr: C, 44.87; H, 7.99; N, 8.02. Found: C, 44.76; H, 7.03; N, 7.40. [(5,15-Bis{4-methoxycarbonylphenyl}porphyrin-10-yl)phosphonic acid](bromo)indium(III) Bis(triethylammonium) Salt (In-4c). The complex was prepared from In-1c (0.013 g, 0.0151 mmol) in 1.7 mL of CH2Cl2. The target complex was insoluble in organic solvents and, thus, characterized with NMR and UV−vis spectroscopies as a sodium salt, which was obtained in situ by the addition of a saturated solution of NaOH in D2O and H2O, respectively. 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O, 25 °C): δH 10.89 (d, 3 JH,H = 4.8 Hz, 2H, Hβ), 10.37 (s, 1H, Hmeso), 9.44 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.95 (d, 3JH,H = 4.4 Hz, 2H, Hβ), 8.85 (d, 3JH,H = 4.8 Hz, 2H, Hβ), 8.34 and 8.19 (AB system, JAB = 8.0 Hz, 8H, m-Ph and o-Ph, respectively), 4.00 (s, 6H, CO2CH3). 31P NMR (600 MHz, CDCl3/ CD3OD, 2:1, v/v, + 1 drop of a saturated solution of NaOH in D2O in D 2 O, 25 °C): δ P 12.0. MS (MALDI-TOF). Calcd for C72H49In2N8O14P2 ([{M − Br − H}2 + H]+): m/z 1541.1. Found: m/z 1541.4. HRMS (ESI). Calcd for C36H25InN4O7P ([M − Br]+): m/z 771.04942. Found: m/z 771.05063. UV−vis [CHCl3/CH3OH, 50:50, v/v, + 1 drop of a saturated solution of NaOH in H2O): λmax, nm (log ε)]: 420 (5.53), 556 (4.47), 592 (3.84). IR (neat, cm−1): νmax 3365 (br w, OH), 2974 (m), 2931 (m), 2875 (w), 2757 (m), 2737 (m), 2674 (s), 2598 (w), 2489 (m), 2225 (m), 1722 (s, CO), 1716 (m, CO), 1699 (w), 1607 (m), 1475 (m), 1470 (m), 1463 (m), 1455 (w), 1432 (m), 1397 (m), 1383 (w), 1364 (w), 1308 (w), 1277 (s, PO), 1170 (s, PO), 1106 (m), 1067 (m), 1057 (m), 1035 (s), 1010 (s, P−O), 934 (s, P−O), 862 (w), 848 (w), 820 (w), 804 (m), 791 (m), 761 (m), 755 (m), 734 (m), 716 (w), 697 (w), 579 (s), 564 (m), 552 (m). Anal. Calcd for C48H55BrN6O7PIn·4Et3NHBr: C, 48.64; H, 6.75; N, 7.88. Found: C, 48.61; H, 5.61; N, 8.53. [5,15-Bis(p-tolyl)porphyrinato(2−)](bromo)gallium(III) (Ga-5b). A round-bottom flask was charged with Ga-1b (0.010 g, 0.014 mmol), dry dimethylformamide (2 mL), and TMSBr (111 mL, 0.84 mmol) under a continuous flow of argon. The solution was stirred at room temperature for 1 day. The reaction mixture was evaporated to dryness under reduced pressure. Then 5 mL of MeOH was added, and the solution was stirred for an additional 10 min. After removal of the solvent, the resulting crude solid was chromatographed using a CHCl3/CH3OH (90:10, v/v) mixture as an eluent to give Ga-5b as a red-violet crystalline powder in 44% yield (0.004 g). 1H NMR (600 MHz, CDCl3/CD3OD, 2:1, v/v, 25 °C): δH 10.38 (s, 2H, Hmeso), 9.43 (d, 3JH,H = 4.7 Hz, 4H, Hβ), 9.13 (d, 3JH,H = 4.7 Hz, 4H, Hβ), 7.91 (d, 3 JH,H = 7.9 Hz, 4H, o-Ph), 7.44 (d, 3JH,H = 7.8 Hz, 4H, m-Ph), 2.55 (s, 6H, CH3). HRMS (ESI). Calcd for C34H24GaN4 ([M − Br]+) m/z 557.12513. Found: m/z 557.12509. UV [CHCl3; λmax, nm (log ε)]: 410 (5.47), 540 (4.21), 578 (3.66). IR (neat, cm−1): νmax 2939 (w), 2921 (m), 2855 (m), 1717 (w), 1699 (w), 1575 (w), 1533 (w), 1508 (m), 1455 (w), 1393 (m), 1326 (w), 1300 (w), 1270 (w), 1212 (m), 1180 (m), 1148 (m), 1106 (w), 1065 (m), 1000 (s), 915 (w), 853 (m), 800 (m), 787 (s), 753 (m), 730 (m), 698 (m), 668 (m), 588 (w), 575 (w), 566 (m), 554 (m).
Article
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b03160. HRMS (ESI) and MALDI-TOF MS spectra, UV−vis spectra, and NMR spectra for synthesized compounds and additional data on the X-ray structures (PDF) X-ray crystallographic data in CIF format (CIF) X-ray crystallographic data in CIF format (CIF) X-ray crystallographic data in CIF format (CIF) X-ray crystallographic data in CIF format (CIF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected]. *E-mail:
[email protected]. ORCID
Yulia G. Gorbunova: 0000-0002-2333-4033 Roger Guilard: 0000-0001-7328-3695 Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS This work was supported by the CNRS, RAS, the Russian Foundation for Basic Research (Grant N 12-03-93110) and carried out in the framework of the International Associated French−Russian Laboratory of Macrocyclic Systems and Related Materials (LIA LAMREM) of CNRS and RAS. M.V.V. is grateful to the French government for Joint Supervision Ph.D. Grants.
■
REFERENCES
(1) Beletskaya, I. P.; Tyurin, V. S.; Tsivadze, A. Y.; Guilard, R.; Stern, C. Supramolecular Chemistry of Metalloporphyrins. Chem. Rev. 2009, 109, 1659−1713. (2) Drain, C. M.; Varotto, A.; Radivojevic, I. Self-Organized Porphyrinic Materials. Chem. Rev. 2009, 109, 1630−1658. (3) Bessmertnykh-Lemeune, A. G.; Guilard, R.; Stern, C.; Yu, Y.; Enakieva, Y. G. G.; Nefedov, A. Y. T.; Biomimetic, S. E. Studies of Porphyrin Self-Assembled Systems. In Supramolecular Systems: Chemistry, Types and Applications; Pena, C., Ed.; Nova Science: Hauppauge, NY, 2016. (4) Stuzhin, P. A.; Goeldner, M.; Homborg, H.; Semeikin, A. S.; Migalova, I. S.; Wolowiec, S. Diazaporphyrins: Synthesis, Characterization and X-Ray Crystal Structure of (3,7,13,17-Tetramethyl2,8,12,18-Tetrabutyl-5,15-diazaporphinato)chloroindium(III). Mendeleev Commun. 1999, 9, 134−136. (5) Mal’chugina, O. V.; Stuzhin, P. A. Synthesis and Study of Organometallic Complexes of octaphenyltetraazaporphyrinatoindium(III). Russ. Chem. Bull. 2002, 51, 2261−2267. (6) Stuzhin, P. A.; Nefedov, S. E.; Kumeev, R. S.; Ul-Haq, A.; Minin, V. V.; Ivanova, S. S. Effects of Solvation on the Spin State of Iron(III) in 2,8,12,18-Tetrabutyl-3,7,13,17-Tetramethyl-5,10diazaporphyrinatoiron(III) Chloride. Inorg. Chem. 2010, 49, 4802− 4813. (7) Meininger, D. J.; Chee-Garza, M.; Arman, H. D.; Tonzetich, Z. J. Gallium(III) Tetraphenylporphyrinates Containing Hydrosulfide and Thiolate Ligands: Structural Models for Sulfur-Bound Iron(III) Hemes. Inorg. Chem. 2016, 55, 2421−2426. (8) Bohle, D. S.; Dodd, E. L. [Gallium(III) Protoporphyrin IX]2: A Soluble Diamagnetic Model for Malaria Pigment. Inorg. Chem. 2012, 51, 4411−4413.
N
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry (9) Bohle, D. S.; Dodd, E. L.; Pinter, T. B. J.; Stillman, M. J. Soluble Diamagnetic Model for Malaria Pigment: Coordination Chemistry of gallium(III)protoporphyrin-IX. Inorg. Chem. 2012, 51, 10747−10761. (10) Dodd, E. L.; Bohle, D. S. Extended Structure of indium(III) Protoporphyrin IX Acetate Mimics Dimer Structure of Hematin Anhydride. Polyhedron 2016, 108, 36−42. (11) Balch, A. L.; Noll, B. C.; Olmstead, M. M.; Reid, S. M. A Cofacial, Dimeric, Metallaoxophlorin Complex: [lndium(III) (octaethyloxophlorin)]2. J. Chem. Soc., Chem. Commun. 1993, 1088− 1090. (12) Garcia, T. Y.; Olmstead, M. M.; Fettinger, J. C.; Balch, A. L. Cleavage of the indium(III) Octaethyloxophlorin Dimer, {In(III) (OEPO)}2, with Lewis Bases. Importance of Outer-Sphere Hydrogen Bonding in Adduct Structures. Inorg. Chem. 2008, 47, 11417−11422. (13) Steinle, E. D.; Amemiya, S.; Buhlmann, P.; Meyerhoff, M. E. Origin of Non-Nernstian Anion Response Slopes of MetalloporphyrinBased Liquid/polymer Membrane Electrodes. Anal. Chem. 2000, 72, 5766−5773. (14) Malinowska, E.; Niedziółka, J.; Meyerhoff, M. E. Potentiometric and Spectroscopic Characterization of Anion Selective Electrodes Based on metal(III) Porphyrin Ionophores in Polyurethane Membranes. Anal. Chim. Acta 2001, 432, 67−78. (15) Wang, E.; Romero, C.; Santiago, D.; Syntilas, V. Optical Anion Sensing Characteristics of Indium-Porphyrin and Lipophilic Dichlorofluorescein Doped Polymer Films. Anal. Chim. Acta 2001, 433, 89−95. (16) Zhang, W.; Roźniecka, E.; Malinowska, E.; Parzuchowski, P.; Meyerhoff, M. Optical Chloride Sensor Based on Dimer-Monomer Equilibrium of Indium (III)-Octaethylporphyrin in Polymeric Film. Anal. Chem. 2002, 74, 4548−4557. (17) Witowska-Jarosz, J.; Górski, Ł.; Malinowska, E.; Jarosz, M. Mass Spectrometric Investigation of Gallium and Zirconium Complexes with Octaethylporphyrin and Tetraphenylporphyrin. J. Mass Spectrom. 2002, 37, 1236−1241. (18) Parzuchowski, P. G.; Kampf, J. W.; Roźniecka, E.; Kondratenko, Y.; Malinowska, E.; Meyerhoff, M. E. Gallium(III) and indium(III) Octaethylporphyrin Dimeric Complexes with a Single μ-Hydroxo Bridge: Synthesis, Structure and Stability in Anion-Containing Organic Media. Inorg. Chim. Acta 2003, 355, 302−313. (19) Guilard, R.; Barbe, J. M.; Richard, P.; Petit, P.; Andre, J. J.; Lecomte, C.; Kadish, K. M. Electrocrystallization and X-Ray Structure of Partially Oxidized Stacked Porphyrin Trimers of the Form [(OEP)Ga]3F2(BF4)2.cntdot.C7H8. J. Am. Chem. Soc. 1989, 111, 4684−4687. (20) Wojaczynski, J.; Latos-Grazynski, L. Synthesis and Characterization of Gallium(III) 2-Hydroxy-5,10,15,20-Tetraphenylporphyrin. A Novel Example of a Cyclic Gallium(III) Porphyrin Trimer. Inorg. Chem. 1995, 34, 1054−1062. (21) Cocolios, P.; Fournari, P.; Guilard, R.; Lecomte, C.; Protas, J.; Boubel, J. C. Synthesis and Physicochemical Characteristics of Alkane (or Arene)-Thio-, -Sulphinato-, and -Sulphonato-indium(III) Porphyrins. Crystal Structure of methanesulphonato(5,10,15,20tetraphenylporphyrinato)indium(III). J. Chem. Soc., Dalton Trans. 1980, 2081−2089. (22) Goulon, J.; Friant, P.; Goulon-Ginet, C.; Coutsolelos, A.; Guilard, R. Bridge-Stacked Polymeric Structure of a Fluorinated Ga(III) Porphyrin Deduced from a Perturbed Difference Fourier Analysis of EXAFS Spectra. Chem. Phys. 1984, 83, 367−375. (23) Bryden, F.; Boyle, R. W. Metalloporphyrins for Medical Imaging Applications. Advances in Inorganic Chemistry; Elsevier Inc.: New York, 2016; Vol. 68, pp 141−221. (24) Bryden, F.; Savoie, H.; Rosca, E. V.; Boyle, R. W. PET/PDT Theranostics: Synthesis and Biological Evaluation of a PeptideTargeted Gallium Porphyrin. Dalt. Trans. 2015, 44, 4925−4932. (25) Bhadwal, M.; Das, T.; Dev Sarma, H.; Banerjee, S. Radiosynthesis and Bioevaluation of [68Ga]-Labeled 5,10,15,20-Tetra(4Methylpyridyl)-Porphyrin for Possible Application as a PET Radiotracer for Tumor Imaging. Mol. Imaging Biol. 2015, 17, 111−118.
(26) Alberti, G. Syntheses,Crystalline Structure, and Ion-Exchange Properties of Insoluble Acid Salts of Tetravalent Metals and Their Salt Forms. Acc. Chem. Res. 1978, 11, 163−170. (27) Cao, G.; Hong, H. G.; Mallouk, T. E. Layered Metal Phosphates and Phosphonates: From Crystals to Monolayers. Acc. Chem. Res. 1992, 25, 420−427. (28) Cabeza, A.; Aranda, M. A. G.; Bruque, S. Structural Complexity and Metal Coordination Flexibility in Two Acetophosphonates. J. Mater. Chem. 1998, 8, 2479−2485. (29) Clearfield, A.; Wang, Z. Organically Pillared Microporous Zirconium Phosphonates. J. Chem. Soc. Dalt. Trans. 2002, 2937−2947. (30) Matano, Y.; Matsumoto, K.; Terasaka, Y.; Hotta, H.; Araki, Y.; Ito, O.; Shiro, M.; Sasamori, T.; Tokitoh, N.; Imahori, H. Synthesis, Structures, and Properties of Meso-Phosphorylporphyrins: SelfOrganization through P-Oxo-Zinc Coordination. Chem. - Eur. J. 2007, 13, 891−901. (31) Atefi, F.; McMurtrie, J. C.; Arnold, D. P. Multiporphyrin Coordination Arrays Based on Complexation of magnesium(II) Porphyrins with Porphyrinylphosphine Oxides. Dalton Trans. 2007, 2163−2170. (32) Atefi, F.; McMurtrie, J. C.; Turner, P.; Duriska, M.; Arnold, D. P. Meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric {[10,20-diphenylporphyrinatonickel(II)-5,15-Diyl]-Bis[P(O)Ph(2)] and Polymeric Self-Coordinated {[10,20-Diphenylporphyrinat. Inorg. Chem. 2006, 45, 6479−6489. (33) Enakieva, Y. Y.; Bessmertnykh, A. G.; Gorbunova, Y. G.; Stern, C.; Rousselin, Y.; Tsivadze, A. Y.; Guilard, R. Synthesis of MesoPolyphosphorylporphyrins and Example of Self-Assembling. Org. Lett. 2009, 11, 3842−3845. (34) Vinogradova, E. V.; Enakieva, Y. Y.; Nefedov, S. E.; Birin, K. P.; Tsivadze, A. Y.; Gorbunova, Y. G.; Bessmertnykh-Lemeune, A. G.; Stern, C.; Guilard, R. Synthesis and Self-Organization of Zinc β(Dialkoxyphosphoryl)porphyrins in the Solid State and in Solution. Chem. - Eur. J. 2012, 18, 15092−15104. (35) Sinelshchikova, A. A.; Nefedov, S. E.; Enakieva, Y. Y.; Gorbunova, Y. G.; Tsivadze, A. Y.; Kadish, K. M.; Chen, P.; Bessmertnykh-Lemeune, A. G.; Stern, C.; Guilard, R. Unusual Formation of a Stable 2D Copper Porphyrin Network. Inorg. Chem. 2013, 52, 999−1008. (36) Fang, Y.; Kadish, K. M.; Chen, P.; Gorbunova, Y. G.; Enakieva, Y. Y.; Tsivadze, A. Y.; Bessmertnykh-Lemeune, A. G.; Guilard, R. Electrochemical and Spectroelectrochemical Studies of β-Phosphorylated Zn Porphyrins. J. Porphyrins Phthalocyanines 2013, 17, 1035− 1045. (37) Zubatyuk, R. I.; Sinelshchikova, A. A.; Enakieva, Y. Y.; Gorbunova, Y. G.; Tsivadze, A. Y.; Nefedov, S. E.; BessmertnykhLemeune, A. G.; Guilard, R.; Shishkin, O. V. Insights into the Crystal Packing of Phosphorylporphyrins Based on the Topology of Their Intermolecular Interaction Energies. CrystEngComm 2014, 16, 10428− 10438. (38) Uvarova, M. A.; Sinelshchikova, A. A.; Golubnichaya, M. A.; Nefedov, S. E.; Enakieva, Y. Y.; Gorbunova, Y. G.; Tsivadze, A. Y.; Stern, C.; Bessmertnykh-Lemeune, A. G.; Guilard, R. Supramolecular Assembly of Organophosphonate Diesters Using Paddle-Wheel Complexes: First Examples in Porphyrin Series. Cryst. Growth Des. 2014, 14, 5976−5984. (39) Bhatti, M.; Bhatti, W.; Mast, E. Preparation of Indium (III) Tetraphenylporphine Complexes. Inorg. Nucl. Chem. Lett. 1972, 8, 133−137. (40) Eaton, S. S.; Eaton, G. R. Effects of Para Substituent and Metal Ion on Rates of Phenyl Ring Rotation in Ruthenium, Indium, and Titanium Complexes of Para-Substituted Tetraphenylporphyrins. J. Am. Chem. Soc. 1977, 99, 6594−6599. (41) Coutsolelos, A.; Guilard, R.; Boukhris, A.; Lecomte, C. Synthesis and Characterisation of Azido- and Thiocyanato-gallium(III) Porphyries. Crystal Structure of azido(2,3,7,8,12,13,17,18-Octaethylporphyrinato)gallium(III). J. Chem. Soc., Dalton Trans. 1986, 1779. O
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry (42) Kadish, K. M.; Cornillon, J. L.; Coutsolelos, A.; Guilard, R. Synthesis, Electrochemistry, and Ligand-Addition Reactions of gallium(III) Porphyrins. Inorg. Chem. 1987, 26, 4167−4173. (43) Enakieva, Y. Y.; Michalak, J.; Abdulaeva, I. A.; Volostnykh, M. V.; Stern, C.; Guilard, R.; Bessmertnykh-Lemeune, A. G.; Gorbunova, Y. G.; Tsivadze, A. Y.; Kadish, K. M. General and Scalable Approach to A 2 B- and A 2 BC-Type Porphyrin Phosphonate Diesters. Eur. J. Org. Chem. 2016, 2016, 4881−4892. (44) McKenna, C. E.; Schmidhuser, J. Functional Selectivity in Phosphonate Ester Dealkylation with Bromotrimethylsilane. J. Chem. Soc., Chem. Commun. 1979, 739. (45) Nixon, C. M.; Le Claire, K.; Odobel, F.; Bujoli, B.; Talham, D. R. Palladium Porphyrin Containing Zirconium Phosphonate Langmuir−Blodgett Films. Chem. Mater. 1999, 11, 965−976. (46) McKenna, C. E.; Higa, M. T.; Cheung, N. H.; McKenna, M.-C. The Facile Dealkylation of Phosphonic Acid Dialkyl Esters by Bromotrimethylsilane. Tetrahedron Lett. 1977, 18, 155−158. (47) Borbas, K. E.; Kee, H. L.; Holten, D.; Lindsey, J. S. A Compact Water-Soluble Porphyrin Bearing an Iodoacetamido Bioconjugatable Site. Org. Biomol. Chem. 2008, 6, 187−194. (48) Borbas, K. E.; Mroz, P.; Hamblin, M. R.; Lindsey, J. S. Bioconjugatable Porphyrins Bearing a Compact Swallowtail Motif for Water Solubility. Bioconjugate Chem. 2006, 17, 638−653. (49) Boduszek, B.; Olszewski, T. K.; Goldeman, W.; Grzegolec, K.; Blazejewska, P. Preparation of New Imidazol-2-Yl-(Amino)methylphosphonates, Phosphinates and Phosphine Oxides and Their Unexpected Cleavage under Acidic Conditions. Tetrahedron 2012, 68, 1223−1229. (50) Michalska, J.; Boduszek, B.; Olszewski, T. K. New Quinoline-2, −3, and 4-Yl-(Amino) Methylphosphonates: Synthesis and Study on the C-P Bond Cleavage in Quinoline-2 and −4 Derivatives under Acidic Conditions. Heteroat. Chem. 2011, 22, 617−624. (51) Olszewski, T. K.; Boduszek, B. Synthesis of New Thiazole-2, −4, and −5-Yl-(Amino)methylphosphonates and Phosphinates: Unprecedented Cleavage of Thiazole-2 Derivatives under Acidic Conditions. Tetrahedron 2010, 66, 8661−8666. (52) Doskocz, M.; Roszak, S.; Gancarz, R. The Decomposition of αAminophosphine Oxides to Phosphonic Acid Derivatives (PIII). J. Mol. Model. 2008, 14, 435−440. (53) Doskocz, M.; Roszak, S.; Majumdar, D.; Doskocz, J.; Gancarz, R.; Leszczynski, J. Theoretical Studies on the Mechanism of C−P Bond Cleavage of a Model α-Aminophosphonate in Acidic Condition †. J. Phys. Chem. A 2008, 112, 2077−2081. (54) Ivanova, S. S.; Stuzhin, P. A. Unusual Catalytic Effect of Halide Anions in the Protolytic Dissociation of indium(III) Octaphenyltetraazaporphyrins. Mendeleev Commun. 2003, 13, 17−18. (55) Ivanova, S. S.; Stuzhin, P. a. Indium(III) Complexes of Octaphenylporphyrazine: Effect of Halide Coordination on the Basic Properties and Stability in Acid Media. J. Porphyrins Phthalocyanines 2011, 15, 1299−1309. (56) Godziela, G. M.; Tilotta, D.; Goff, H. M. Synthesis and Magnetic Resonance Spectroscopy of Novel Phenolato-Bridged manganese(III) and iron(III)-manganese(III) Porphyrin Complexes. Inorg. Chem. 1986, 25, 2142−2146. (57) Goff, H. M.; Shimomura, E. T.; Lee, Y. J.; Scheidt, W. R. Synthesis, Molecular Structure, and Solution Properties of a Phenolate-Bridged (tetraarylporphinato)iron(III) Dimer. Inorg. Chem. 1984, 23, 315−321. (58) Ball, R. G.; Lee, K. M.; Marshall, A. G.; Trotter, J. Crystal and Molecular Structure of (5,10,15,20-tetraphenylporphinato)indium(III) Chloride. Inorg. Chem. 1980, 19, 1463−1469. (59) Bedel-Cloutour, C. H.; Mauclaire, L.; Pereyre, M.; Adams, S.; Drager, M. Crystal and Molecular Structure of 10-(4′-N-Pyridyl)5,15,20-Triphenylporphinato indium(III) Chloride. Polyhedron 1990, 9, 1297−1303. (60) Garcia, T. Y.; Olmstead, M. M.; Fettinger, J. C.; Balch, A. L. Crystallization of Chloroindium(iii)octaethylporphyrin into a Clamshell Motif to Engulf Guest Molecules. CrystEngComm 2010, 12, 866− 871.
(61) Raptopoulou, C.; Daphnomili, D.; Karamalides, A.; Di Vaira, M.; Terzis, A.; Coutsolelos, A. G. Perhalogenated Porphyrinic Derivatives with Indium and Thallium: The X-Ray Structures of (β-Cl4TPP)Tl(Cl), (β-Cl4TPP)In(Cl) and (TpFTPP)Tl(Cl). Polyhedron 2004, 23, 1777−1784. (62) Hsieh, Y.; Sheu, Y.; Liu, I.; Lin, C.-C.; Chen, J.; Wang, S.; Lin, H. Structure of Acetato(meso-5,10,15,20-tetraphenylporphyrinato)gallium(III): Ga(tpp) (OAc). J. Chem. Crystallogr. 1996, 26, 203−207. (63) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals, 3rd ed.; Pergamon Press: Oxford, U.K., 1988. (64) APEX2, version 2014.11-0; Bruker AXS Inc.: Madison, WI, 2014. (65) SADABS, version 2014/5; Bruker AXS Inc.: Madison, WI, 2014. (66) SAINT, version 8.34A; Bruker AXS Inc.: Madison, WI, 2013. (67) SHELXTL, version 6.14; Bruker AXS Inc.: Madison, WI, 2003.
P
DOI: 10.1021/acs.inorgchem.6b03160 Inorg. Chem. XXXX, XXX, XXX−XXX
