Assembly, Disassembly, and Reassembly ... - ACS Publications

Jan 26, 2015 - A strategy based on assembly−disassembly−reassembly processes for the conversion of self-assembled dipyrrin-based Ni(II) (Ni(dpm)2)...
0 downloads 0 Views 3MB Size
Article pubs.acs.org/IC

Assembly, Disassembly, and Reassembly: Conversion of Homometallic Coordination Networks into Mixed Metal−Organic Frameworks Antoine Béziau,† Stéphane A. Baudron,*,† Guillaume Rogez,‡ and Mir Wais Hosseini*,† †

Laboratoire de Tectonique Moléculaire, UMR UdS-CNRS 7140, icFRC, Université de Strasbourg, 4 Rue Blaise Pascal, F-67000, Strasbourg, France ‡ Institut de Physique et Chimie des Matériaux de Strasbourg, UMR UdS-CNRS, 7504, Strasbourg, France S Supporting Information *

ABSTRACT: A strategy for the conversion of homometallic coordination networks into mixed metal−organic frameworks (MM′MOFs) is proposed. Ni(II) complexes of dipyrrin (dpm) ligands bearing peripheral pyridyl or imidazolyl units have been shown to self-assemble into coordination polymers with the metal cation in an octahedral environment coordinated to two bis-pyrrolic chelates and two neutral monodentate coordinating units such as pyridyl or imidazolyl moieties. Taking advantage of the chelate effect, the two monodentate units may be replaced by a diimine ligand leading to the disassembly of the networks by the formation of discrete soluble complexes. The latter can be employed as metallatectons for the construction of heterometallic architectures upon reaction with a secondary metal salt. This approach was applied using either 1,10-phenanthroline (phen) or 2,2′-bipyrimidine (bpm) as chelates leading to a series of mono- and binuclear metallatectons of the (phen)Ni(dpm)2 and (bpm)[Ni(dpm)2]2 type. Subsequent assembly with CdCl2 afforded either interpenetrated 2D grid-type architectures or 3D MM′MOFs.



INTRODUCTION Fueled by applications in gas storage, catalysis, sensing, and detection, the field of coordination networks (CNs) and metal−organic frameworks (MOFs) has emerged over the past decades as an active research area.1 These architectures are constructed by association of metal centers or complexes with polytopic organic ligands. Regarding the latter, carboxylate, azole, and pyridyl derivatives as well as combinations thereof have been extensively exploited.2 Dipyrrins (dpms) represent another class of species of interest.3 These bis-pyrrolic compounds can be readily functionalized and form, under mild basic conditions, monoanionic chelates leading to a variety of metal complexes. Thus, when the dipyrrin is appended with an additional peripheral coordinating group, its association with metal centers generates metallatectons4 or metalloligands5 prone to self-assembly for the formation of CNs. Both homoand heterometallic architectures (MOFs and mixed metal− organic frameworks, MM′MOFs, respectively) have thus been prepared.6−10 MM′MOFs obtained by reaction of a dpm based metallatecton with a second metal center, such as Ag(I) and Cd(II) salts, have been reported.6−8 On the other hand, homometallic MOFs are obtained by self-assembly of complexes incorporating a cation capable of increasing its coordination number (see Scheme 1) such as (acacR)Cu(dpm) (acacR = acetylacetonate derivatives)9 or Cd(dpm)2 and Ni(dpm)2 complexes with dipyrrin ligands bearing a pyridyl © XXXX American Chemical Society

or phenylimidazolyl moiety (for example, derivatives 1−3, Scheme 2).10 In the crystalline state, the metal cation is bound not only to the chelates but also to the coordinating unit introduced at the periphery of the dpm ligand of a neighboring complex, leading to an infinite network. These homometallic CNs may be converted into heterometallic ones by disassembling the infinite structures via decoordination of the peripheral neutral unit into a discrete (soluble) metallatecton, and subsequent reassembling with a second metal cation (see Scheme 1). In the case of (acacR)Cu(dpm) species, the disassembly process can be directly achieved upon solubilization of the complex and subsequent addition of M′ salt leads to MM′MOFs.7 In contrast, Cd(dpm)2 and Ni(dpm)2 complexes are rather insoluble in common organic solvents preventing the synthesis of MM′MOFs.10 Since within the extended architecture the Cd(II) or Ni(II) cation, adopting an octahedral coordination geometry, is bound to two dpm as well as to two pyridyl or imidazolyl groups belonging to two consecutive complexes, it should be possible to bring these metallatectons into solution upon breaking the coordination network using a neutral chelate unit such as a diimine ligand. Indeed, owing to the chelate effect, the two neutral monodentate moieties may Received: December 10, 2014

A

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Scheme 1. Assembly−Disassembly−Reassembly Strategy for the Formation of MM′MOF

Scheme 2. Representation of a Dipyrrin and Pyridyl- and Imidazolyl-Appended Ligands 1−3

Scheme 3. Synthetic Pathway for the Preparation of Complexes 7−10

be replaced by the chelating ligand, affording thus discrete heteroleptic octahedral complexes bearing two peripheral binding units available for binding of a second metal center leading to MM′MOFs (see Scheme 1). To our knowledge, this strategy has not been explored so far. We report herein on the conversion of infinite coordination networks based on selfassembled Ni(II)−dpm complexes into MM′MOFs using CdCl2 salts through the generation of discrete heteroleptic metallatectons of the (diimine)Ni(dpm)2 type.



Table 1. Selected Average Distances (Å) for Compounds 7− 14

RESULTS AND DISCUSSION Synthesis and Crystal Structure of the Metallatectons. Pyridyl, phenyl-pyridyl, and phenyl-imidazolyl appended dipyrrins 1−3 have been reported to form self-assembled architectures, 4−6, respectively, in the presence of Ni(II) salts (Scheme 3).10 These CNs, insoluble in most common organic solvents, were used for the formation of heteroleptic metallatectons by reaction with a diimine ligand such as phenanthroline or bipyrimidine. A suspension of 4−6 was thus reacted with 1,10-phenanthroline (phen) in CHCl3 leading to a complete dissolution of the solid and formation of discrete mononuclear complexes 7−9 of the (phen)Ni(dpm)2 type, in 84−96% yield. Reaction of the bis-chelating ligand 2,2′bipyrimidine (bpm) with a suspension of MOF 6 in CHCl3 (Scheme 3) led also to the formation of discrete complex 10, a rare example of binuclear dpm based compound,11 in 51% yield. The metallatectons thus obtained were characterized by elemental analysis, single-crystal X-ray diffraction, and UV−vis spectroscopy. For all four compounds, two intense absorption bands between 460 and 500 nm are observed in CH2Cl2. These bands correspond to π−π* ligand centered transitions of the dpm as reported for other Ni(II) dipyrrinato complexes.12 Single-crystals of complexes 7−10 suitable for X-ray diffraction analysis were obtained by n-pentane or diethyl ether vapor diffusion into a concentrated CHCl3 or THF solution of discrete complexes (Tables 1 and 2). For mononuclear compounds 7−9, the Ni(II) cation, in an

7 8 9 10 11 12 13 14

Ni−Ndpm

Ni−Ndiimine

Cd−N

Cd−Cl

Cd···Cd

2.072 2.074 2.068 2.062 2.068 2.074 2.066 2.055

2.136 2.138 2.140 2.181 2.133 2.148 2.156 2.159

2.388 2.417 2.401 2.329

2.585 2.555 2.562 2.617

16.530 25.473 25.395 18.128, 23.470

octahedral environment, is coordinated to two dpm chelates and one phen unit (Figure 1). As expected, both Δ and Λ enantiomers are present within the crystals. As reported for the self-assembled complexes 4−6 and (2,2′-bipyridine)Ru(dpm)2 complexes,10,13 the Ni−N distances are shorter with the dipyrrin chelates than with the diimine ligand (Table 1). It should be noted that, unlike what is observed for other heteroleptic species of the (acetylacetonate)Co(dpm)2 type, no distortion around the N−N hinge of the dpm is present for metallatectons 7−9.8c Binuclear complex 10, crystallizing as a solvate (Table 2), (10)(CHCl3)3, features two Ni(II) cations bridged by a bpm ligand and each coordinated to two dpm chelates with Ni−N distances similar to the ones observed for 7−9 (Figure 1). In B

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Table 2. Crystallographic Data for Complexes 7−10 formula fw cryst syst space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å3 Z T, K μ, mm−1 reflns collected indep reflns (Rint) R1 (I > 2σ(I))a wR2 (I > 2σ(I))a R1 (all data)a wR2 (all data)a GOF a

7(CHCl3)

8(CHCl3)2

9(Et2O)

10(CHCl3)3

C41H29Cl3N8Ni 798.78 triclinic P1̅ 10.4834(5) 12.4258(7) 14.6535(9) 84.733(2) 86.098(2) 71.663(2) 1802.71(17) 2 173(2) 0.804 29 354 9682 (0.0460) 0.0634 0.1629 0.1193 0.1990 1.042

C54H38Cl6N8Ni 1070.33 monoclinic C2/c 16.1335(4) 10.5421(4) 29.7008(9)

C52H44N10NiO 883.68 monoclinic P2/c 14.8638(3) 10.3919(2) 15.4982(3)

105.715(2)

115.8840(10)

4862.7(3) 4 173(2) 0.776 43 373 7010 (0.0408) 0.0498 0.1109 0.0851 0.1292 1.061

2153.74(7) 2 173(2) 0.504 65 828 5828 (0.0386) 0.0435 0.1127 0.0590 0.1272 1.093

C83H61Cl9N20Ni2 1774.99 triclinic P1̅ 13.0316(11) 13.1577(11) 13.6126(11) 76.875(4) 75.376(4) 63.567(3) 2004.6(3) 1 173(2) 0.829 36 158 9881 (0.0582) 0.0898 0.2110 0.1669 0.2578 1.072

R1 = ∑||Fo| − |Fc||/∑|Fo|. wR2 = [∑w(Fo2 − Fc2)2/∑wFo4]1/2.

(1/1) buffer, with a MeOH solution of CdCl2, produced crystals after few days for all metallatectons used, except 9. Metallatecton 7 in DMF led to the formation of MM′MOF 11, [(7)2CdCl2](DMF)2(H2O) (Table 3). The Cd(II) cation is in an octahedral coordination environment with two apical chloride anions and four pyridyl groups of four complexes 7 in the square base. As a result, 2D grid-type networks are formed in the ab plane with Cd(II) cations separated by ca. 16.5 Å (Figure 2 left). This arrangement is reminiscent of square grids observed for [M(dpm)2]2CdCl2 MM′MOFs based on linear bridging complexes.8 However, owing to the octahedral nature of the metallatectons, the 2D sheets are not flat (Figure 2, middle). The cavities present in the grids are occupied by another identical network as a result of double homointerpenetration in a parallel fashion (Figure 2, right). Within each individual grid, both Λ and Δ enantiomers of the Ni(II) complex are present. Analogous reaction starting from metallatecton 8 either in DMF or CH2Cl2 led to the formation of crystals composed of MM′MOFs 12 and 13, respectively, [(8)2CdCl2](solvent) (Table 3). Both compounds differ by the nature of the solvent molecules included in the structure but feature isomorphous coordination networks. Therefore, only 12, [(8)2CdCl2](DMF)6(H2O), will be described hereafter. As observed for 11, the CdCl2 nodes are bridged by Ni(II) complexes (present as both Λ and Δ enantiomers) leading to a similar grid type arrangement, albeit expanded owing to the presence of a phenyl spacer between the dpm chelate and the peripheral pyridyl group in ligand 2. As a consequence, the Cd(II) cations within a grid motif are separated by ca. 25.5 Å (Table 1), and the cavities formed by the network are larger than in the case of 11. Triple interpenetration in a parallel fashion is observed in this case (Figure 2 right). It is interesting to note that the expansion of the network by substituting ligand 2 for 1 has already been observed in the crystal structures of the self-assembled coordination polymers 4 and 5.10a Although MM′MOFs 11−13 present different interpenetration,16 the solvent accessible voids calculated using the PLATON software

Figure 1. Crystal structures of complexes 7−10. Solvent molecules and hydrogen atoms have been omitted for clarity. For 7−9, only the Λ enantiomer is presented.

the analyzed crystal, the complex is present as the meso compound comprising both the Δ and Λ configurations within the molecule. Mixed-Metal Organic Frameworks. For the preparation of heterobimetallic MM′MOFs, metallatectons 7−10 were combined with CdCl2. This salt has been chosen in light of its propensity to form coordination polymers with pyridyl and imidazolyl based ligands and complexes.14,15 In particular, we have reported that association of CdCl2 with homoleptic metallatectons of the M(dpm)2 type (M = Cu(II), Pd(II), and Zn(II)) or heteroleptic (acacR)Co(dpm)2 complexes (dpm = 1 or 2) produces a series of MM′MOFs.8 Layering a DMF or CH2Cl2 solution of 7−10 through a DMF or CH2Cl2/MeOH C

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Table 3. Crystallographic Data for Complexes 11−14 formula fw cryst syst space group a, Å b, Å c, Å β, deg V, Å3 Z T, K μ, mm−1 reflns collected indep reflns (Rint) R1 (I > 2σ(I))a wR2 (I > 2σ(I))a R1 (all data)a wR2 (all data)a GOF a

11

12

13

14

C86H72CdCl2N18Ni2O3 1706.54 monoclinic P2/n 22.2012(5) 8.8143(2) 22.3347(5) 102.1960(10) 4271.99(17) 2 173(2) 0.803 98428 12 552 (0.0590) 0.0584 0.1685 0.0921 0.1930 1.061

C112H116CdCl2N22Ni2O7 2303.09 monoclinic C2/c 32.6713(7) 9.4472(2) 38.4422(8) 107.4430(10) 11319.7(4) 4 173(2) 0.629 254718 14 635 (0.0684) 0.0625 0.1800 0.0771 0.1947 1.084

C106H76CdCl6N16Ni2 2016.35 monoclinic C2/c 32.2015(9) 9.3890(3) 38.2629(12) 106.8590(10) 11071.2(6) 4 173(2) 0.721 100324 15 060 (0.0818) 0.0651 0.1745 0.1011 0.1890 1.047

C95H93CdCl2N25Ni2O5 1965.66 orthorhombic Imm2 23.9011(8) 34.6395(8) 13.4553(3) 11139.9(5) 4 173(2) 0.628 133684 16 239 (0.0571) 0.0383 0.0883 0.0516 0.0917 1.035

R1 = ∑||Fo| − |Fc||/∑|Fo|. wR2 = [∑w(Fo2 − Fc2)2/∑wFo4]1/2.

Figure 2. Portions of the crystal structure of MM′MOFs 11 (top) and 12 (bottom). Top and side views (left and center), interpenetration of the grid-type networks (right). Solvent molecules and hydrogen atoms have been omitted for clarity.

(with a ball of 1.2 Å radius)17 do not differ strikingly: 30%, 35%, and 34%, respectively. Combining metallatecton 10 with CdCl2 in DMF/MeOH mixture as described above afforded crystals of MM′MOF 14, [(10)CdCl2](DMF)5 (Table 3). It should be noted that, as for 13, some solvent molecules present in the crystal are disordered, and therefore, the SQUEEZE command was applied to remove the corresponding electron density for refinement of the structure.17 Here again, the Cd(II) cation is coordinated to two apical chloride anions and four imidazolyl groups belonging to four binuclear complexes, present as meso isomers. As for 11−13, [4 + 4] metallamacrocycles are formed leading to a 3D network (Figure 3) where the Cd(II) centers

are separated by ca. 18.1 and 25.5 Å (Table 1). These cavities are not empty but occupied by two other networks with a triple interpenetration (Figure 3 bottom) with a 48% solvent accessible void calculated using PLATON (1.2 Å radius).17 X-ray powder diffraction study on 11 and 12 shows the presence of a homogeneous single crystalline phase for the different MM′MOFs (Figure 4, top and middle). For 14, a loss of crystalline quality, owing to rapid solvent loss upon removal from the mother liquor, is observed (Figure 4, bottom). Magnetic Properties. Complex 10 and MM′MOF 14 incorporate a bpm bridged binuclear Ni(II) core. In order to investigate the magnetic coupling between the two octahedral cations (S = 1) within this unit, the magnetic properties of both D

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

Figure 4. Simulated (a) and observed (b) PXRD patterns for MM′MOFs 11, 12, and 14. Note that the single-crystal (used for the simulation) and powder data have been collected at different temperatures (173 vs 293 K). The difference in intensities results from preferential orientation.

Figure 3. Two views of the 3D network in the crystal structure of MM’MOF 14 (top) and 3-fold interpenetration (bottom). The three identical 3D networks leading to the interpenetration are differentiated by color. Solvent molecules and hydrogen atoms have been omitted for clarity.

compounds were studied. The measurements were performed under a static applied field of 5 kOe in the 1.8−300 K temperature range. For both compounds, the temperature dependent evolution of the χT value (Figure 5) can be fit using the following spin Hamiltonian H = −J·SNi1·SNi2, thus considering noninteracting dimers within the structures. The fit leads to g = 2.06(1), J = −17.6(1) cm−1, ρ = 4.1(1)% for 10 and g = 2.12(1), J = −18.2(1) cm−1, ρ = 2.1(1)% for 14 with good agreement factors (R = 4 × 10−6 and 1.8 × 10−5, respectively). (g = Landé factor, and ρ = percentage of paramagnetic impurity to account for the increase of χ at low temperature. The presence of such a paramagnetic impurity is common for antiferromagnetic binuclear compounds, and is attributed to the finite size of the crystals and to defects.) These

Figure 5. Temperature dependence of χ (○) and χT (□) for 10 (red) and 14 (green) under a static field of 5 kOe. The solid lines represent the best fit of the data (see text).

values of antiferromagnetic coupling are in agreement with what has been reported for other bpm bridged binuclear complexes of octahedral Ni(II) cations.18 E

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry



λmax (nm)/ε (mol−1 L cm−1): 271 (43 400), 462 (78 900), 500 (35 200). Anal. Calcd for C52H44N10NiO: C, 70.68; H, 5.02; N, 15.85. Found: C, 70.37; H, 4.89; N, 15.64. Single-crystals were obtained by slow vapor diffusion of Et2O into a THF solution of the compound. For complex 10, a CHCl3 (5 mL) solution of 2,2′-bipyrimidine (13.1 mg, 0.08 mmol) was added to a suspension of 7 (104.1 mg, 0.16 mmol) in CHCl3 (25 mL). After the addition of few drops of NEt3, the solution was stirred for 4 days. After filtration and evaporation of the filtrate, MeOH (10 mL) was added to the residue. Upon sonication, centrifugation, and washing with Et2O (2 × 5 mL), 10 was obtained as red solid (60.0 mg, 51%). UV−vis (CH2Cl2) λmax (nm)/ε (mol−1 L cm−1): 329 (30 100), 464 (90 000), 482 (77 400). Anal. Calcd for C80H59Cl3N20Ni2: C, 63.32; H, 3.87; N, 18.23. Found: C, 64.71; H, 4.14; N, 18.57. Single-crystals were obtained by slow vapor diffusion of n-pentane into a CHCl3 solution of the complex. For MM′MOF 11, in a test tube, a DMF (5 mL) solution of 7 (34 mg, 0.05 mmol) was layered with a MeOH (5 mL) solution of CdCl2 (10 mg, 0.05 mmol) separated by a DMF/MeOH (1/1, 2 mL) buffer layer. Red crystals of 11 (14.5 mg, 34%) were harvested after few days. Anal. Calcd for C86H72CdCl2N18Ni2O3: C, 60.53; H, 4.25; N, 14.77. Found: C, 59.28; H, 4.37; N, 14.76. For MM′MOFs 12 and 13, in a test tube, a DMF (5 mL) solution of 8 (35 mg, 0.04 mmol) was layered with a MeOH (4 mL) solution of CdCl2 (8 mg, 0.04 mmol) separated by a DMF/MeOH (1/1, 2 mL) buffer layer. After a few days, red crystals of 12 were obtained (29 mg, 63%). Anal. Calcd for C112H116CdCl2N22Ni2O7: C, 61.62; H, 5.35; N, 14.11. Found: C, 61.79; H, 5.05; N, 13.24. Crystals of 13 were obtained by substituting CH2Cl2 for DMF. For MM′MOF 14, in a test tube, a DMF (20 mL) solution of 10 (34 mg, 0.024 mmol) was layered with a MeOH (2 mL) solution of CdCl2 (4 mg, 0.022 mmol) separated by a DMF/MeOH (1/1, 5 mL) buffer layer. Red crystals of 14 (20 mg) appeared after few days. Anal. Calcd for C95H105CdCl2N25Ni2O11: C, 55.02; H, 5.10; N, 16.88. Found: C, 54.76; H, 4.94; N, 17.13. This formula takes into account six water molecules that have not been refined in the crystal structure determination but have been removed using the SQUEEZE command. X-ray diffraction. Single-crystal data (Tables 2 and 3) were collected on a Bruker SMART CCD diffractometer with Mo Kα radiation. The structures were solved using SHELXS-97 and refined by full matrix least-squares on F2 using SHELXL-97 with anisotropic thermal parameters for all non-hydrogen atoms.19 The hydrogen atoms were introduced at calculated positions and not refined (riding model). For compounds 13 and 14, some solvent molecules present in the structures show high positional disorder. To account for the corresponding electron density, the SQUEEZE command was used.17 CCDC 1037594−1037601 contain the supplementary crystallographic data for compounds 7−14. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. Powder X-ray diffraction diagrams were collected at 293 K on a Bruker D8 diffractometer using monochromatic Cu Kα radiation with a scanning range between 4 and 40° using a scan step of 2°/mn. Magnetic Properties. Magnetic measurements on compounds 10 and 14 were performed using a Quantum Design Squid-VSM magnetometer. Data were corrected for the sample holder, and diamagnetism was estimated from Pascal constants. Magnetization measurements at different fields at room temperature confirm the absence of ferromagnetic impurities.

CONCLUSION A strategy based on assembly−disassembly−reassembly processes for the conversion of self-assembled dipyrrin-based Ni(II) coordination networks into mixed metal−organic frameworks has been developed. In the parent homometallic architectures, the Ni(II) cations are in an octahedral environment, coordinated to two bis-pyrrolic chelates and two neutral peripheral monodentate binding units of neighboring complexes. Taking advantage of the chelate effect, a diimine ligand such as 1,10-phenanthroline (phen) or 2,2′-bipyrimidine (bpm) has been used to replace the two pyridyl or imidazolyl monodentate entities leading to the disassembly of the networks and thus to the formation of discrete and soluble complexes of the (phen)Ni(dpm)2 or (bpm)[Ni(dpm)2]2 type. The latter have been employed as metallatectons for the construction of heterometallic architectures upon reaction with CdCl2. Complex 7, incorporating a pyridyl-appended dpm, leads in the presence of CdCl2 to the formation of MM′MOF 11 displaying a 2D grid-type arrangement with double interpenetration. Interestingly, an analogous reaction using the expanded metallatecton 8 led to similar MM′MOFs, 12 and 13, with larger cavities leading to 3-fold interpenetration. The binuclear complex 10 yielded a 3D MM′MOF, 14, with large cavities, also subject to a triple interpenetration. Magnetic studies on the compounds featuring bpm-bridged Ni(II) cations indicated weak antiferromagnetic coupling between the S = 1 metal centers. Future work will focus on the extension of this strategy to other dpm complexes as well as to other selfassembled architectures such as the ones based on acetylacetonate derivatives.



EXPERIMENTAL SECTION

Synthesis. Dipyrrins 1−3 and self-assembled architectures 4−6 were synthesized as described.10a All other reagents and solvents were obtained from commercial sources and used as received. The elemental analyses were performed by the Service Commun d’Analyse of the University of Strasbourg. For complex 7, a CHCl3 (20 mL) solution of 1,10-phenanthroline monohydrate (38.4 mg, 0.19 mmol) was added to a suspension of 4 (92.2 mg, 0.18 mmol) in CHCl3 (20 mL). The mixture was stirred overnight during which it turned into a clear solution. After evaporation to dryness, MeOH (6 mL) was added to the residue. Upon sonication, filtration, and washing with Et2O (6 mL), 7 was obtained as an orange powder (112.6 mg, 89%). UV−vis (CH2Cl2) λmax (nm)/ε (mol−1 L cm−1): 271 (46 200), 463 (90 100), 501 (41 000). Anal. Calcd for C41H29Cl3N8Ni: C, 61.65; H, 3.66; N, 14.03. Found: C, 61.39; H, 3.62; N, 13.98. Single-crystals were obtained by slow vapor diffusion of n-pentane into a CHCl3 solution of the complex. For complex 8, a CHCl3 (10 mL) solution of 1,10-phenanthroline monohydrate (30.6 mg, 0.15 mmol) was added to a suspension of 5 (91.3 mg, 0.14 mmol) in CHCl3 (10 mL). The solution cleared quickly and was stirred overnight. After evaporation, MeOH (10 mL) was added. Upon sonication, filtration, and rinsing with Et2O (6 mL), 8 was isolated as an orange powder (112 mg, 96%). UV−vis (CH2Cl2) λmax (nm)/ε (mol−1 L cm−1): 269 (69 000), 314 (22 500), 462 (78 400), 500 (35 300). Anal. Calcd for C54H38Cl6N8Ni: C, 60.60; H, 3.58; N, 10.33. Found: C, 60.53; H, 3.61; N, 10.33. Single-crystals were obtained by slow vapor diffusion of n-pentane into a CHCl3 solution of the product. For complex 9, a CHCl3 (2 mL) solution of 1,10-phenanthroline monohydrate (8.9 mg, 0.045 mmol) was added to a suspension of 6 (25.8 mg, 0.041 mmol) in CHCl3 (6 mL). The solution cleared quickly and was stirred overnight. After evaporation, MeOH (2 mL) was added. Upon sonication, filtration, and rinsing with Et2O (6 mL), 9 was isolated as an orange powder (28 mg, 84%). UV−vis (CH2Cl2)



ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.



AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. F

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry Notes

(8) (a) Béziau, A.; Baudron, S. A.; Pogozhev, D.; Fluck, A.; Hosseini, M. W. Chem. Commun. 2012, 48, 10313−10315. (b) Béziau, A.; Baudron, S. A.; Fluck, A.; Hosseini, M. W. Inorg. Chem. 2013, 52, 14439−14448. (c) Béziau, A.; Baudron, S. A.; Rasoloarison, D.; Hosseini, M. W. CrystEngComm 2014, 16, 4973−4980. (9) (a) Halper, S. R.; Malachowski, M. R.; Delaney, H. M.; Cohen, S. M. Inorg. Chem. 2004, 43, 1242−1249. (b) Halper, S. R.; Cohen, S. M. Angew. Chem., Int. Ed. 2004, 43, 2385−2388. (c) Do, L.; Halper, S. R.; Cohen, S. M. Chem. Commun. 2004, 2662−2663. (d) Halper, S. R.; Cohen, S. M. Inorg. Chem. 2005, 44, 4139−4141. (e) Heinze, K.; Reinhart, A. Inorg. Chem. 2006, 45, 2695−2703. (10) (a) Béziau, A.; Baudron, S. A.; Rogez, G.; Hosseini, M. W. CrystEngComm 2013, 15, 5980−5985. (b) Béziau, A.; Baudron, S. A.; Guenet, A.; Hosseini, M. W. Chem.Eur. J. 2013, 19, 3215−3223. (11) (a) Miao, Q.; Shin, J.-Y.; Patrick, B. O.; Dolphin, D. Chem. Commun. 2009, 2541−2543. (b) Tsuchiya, M.; Sakamoto, R.; Kusaka, S.; Kitagawa, Y.; Okumura, M.; Nishihara, H. Chem. Commun. 2014, 50, 5881−5883. (12) (a) Brückner, C.; Karunaratne, V.; Rettig, S. J.; Dolphin, D. Can. J. Chem. 1996, 74, 2182−2193. (b) Gill, H. S.; Finger, I.; Božidarević, I.; Szydlo, F.; Scott, M. J. New J. Chem. 2005, 29, 68−71. (c) Wilson, C. J.; James, L.; Mehl, G. H.; Boyle, R. W. Chem. Commun. 2008, 4582−4584. (d) Choi, S. H.; Kim, K.; Jeon, J.; Meka, B.; Bucella, D.; Pang, K.; Khatua, S.; Lee, J.; Churchill, D. G. Inorg. Chem. 2008, 47, 11071−11083. (e) Yadav, M.; Kumar, P.; Singh, A. K.; Ribas, J.; Pandey, D. S. Dalton Trans. 2009, 9929−9934. (f) Pogozhev, D.; Baudron, S. A.; Hosseini, M. W. CrystEngComm 2010, 12, 2238−2244. (g) Hashimoto, T.; Nishimura, T.; Lin, J. M.; Khim, D.; Maeda, H. Chem.Eur. J. 2010, 16, 11653−11661. (h) Artigau, M.; Bonnet, A.; Ladeira, S.; Hoffmann, P.; Vigroux, A. CrystEngComm 2011, 13, 7149− 7152. (i) Hiang, K.-L.; Bellec, N.; Guerro, M.; Camerel, F.; Roisnel, T.; Lorcy, D. Tetrahedron 2011, 67, 8740−8746. (j) Gupta, R. K.; Pandey, R.; Singh, R.; Srivastava, N.; Maiti, B.; Saha, S.; Li, P.; Xu, Q.; Pandey, D. S. Inorg. Chem. 2012, 51, 8916−8930. (k) Maeda, H.; Nishimura, T.; Akuta, R.; Takaishi, K.; Uchiyama, M.; Muranaka, A. Chem. Sci. 2013, 4, 1204−1213. (l) Maeda, H.; Akuta, R.; Bando, Y.; Takaishi, K.; Uchiyama, M.; Muranaka, A.; Tohnai, N.; Seki, S. Chem.Eur. J. 2013, 19, 11676−11685. (13) (a) Smalley, S. J.; Waterland, M. R.; Telfer, S. G. Inorg. Chem. 2009, 48, 13−15. (b) Hall, J. D.; McLean, T. M.; Smalley, S. J.; Waterland, M. R.; Telfer, S. G. Dalton Trans. 2010, 39, 437−445. (c) Li, G.; Ray, L.; Glass, E. N.; Kovnir, K.; Khoroshutin, A.; Gorelsky, S. I.; Shatruk, M. Inorg. Chem. 2012, 51, 1614−1624. (14) (a) Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc. 1994, 116, 1151−1152. (b) Loï, M.; Graf, E.; Hosseini, M. W.; De Cian, A.; Fischer, J. Chem. Commun. 1999, 603−604. (c) Abrahams, B. F.; Hoskins, B. F.; Robson, R.; Slizys, D. A. CrystEngComm 2002, 4, 478−482. (d) Davidson, G. J. E.; Loeb, S. J. Angew. Chem., Int. Ed. 2003, 42, 74−77. (e) Zhu, H.−F.; Zhao, W.; Okamura, T.; Fan, J.; Sun, W.−Y.; Ueyama, N. New J. Chem. 2004, 28, 1010−1018. (f) Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, 8940− 8341. (g) Plater, M. J.; Gelbrich, T.; Hursthouse, M. B.; De Silva, B. M. CrystEngComm 2006, 8, 895−903. (h) Zheng, S.−R.; Yang, Q.−Y.; Liu, Y.−R.; Zhang, J.−Y.; Tong, Y.−X.; Zhao, C.−Y.; Su, C.−Y. Chem. Commun. 2008, 356−358. (i) Constable, E. C.; Zhang, G.; Housecroft, C. E.; Neuburger, M.; Zampese, J. A. CrystEngComm 2009, 11, 2279− 2281. (j) Ovsyannikov, A.; Ferlay, S.; Solovieva, S. E.; Antipin, I. S.; Konovalov, A. I.; Kyritsakas, N.; Hosseini, M. W. CrystEngComm 2014, 16, 3765−3772. (15) (a) Chen, B.; Fronczek, F. R.; Maverick, A. W. Inorg. Chem. 2004, 43, 8209−8211. (b) Vreshch, V. D.; Lysenko, A. B.; Chernega, A. N.; Howard, J. A. K.; Krautscheid, H.; Sieler, J.; Domasevitch, K. V. Dalton Trans. 2004, 2899−2903. (c) Deiters, E.; Bulach, V.; Hosseini, M. W. New J. Chem. 2006, 30, 1289−1294. (d) Vreshch, V. D.; Lysenko, A. B.; Chernega, A. N.; Sieler, J.; Domasevitch, K. V. Polyhedron 2008, 24, 917−926. (e) Deiters, E.; Bulach, V.; Hosseini, M. W. New J. Chem. 2008, 32, 99−104. (f) Zou, C.; Zhang, Z.; Xu, X.; Gong, Q.; Li, J.; Wu, C.-D. J. Am. Chem. Soc. 2012, 134, 87−90.

The authors declare no competing financial interest.



ACKNOWLEDGMENTS We thank the Université de Strasbourg, the Institut Universitaire de France, the International centre for Frontier Research in Chemistry (icFRC), the C.N.R.S., and the Ministère de l’Enseignement Supérieur et de la Recherche (Ph.D. fellowship to A.B.) for financial support.



REFERENCES

(1) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460−1494. (b) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319−330. (c) Kitagawa, S.; Kitaura, R.; Noro, S. I. Angew. Chem., Int. Ed. 2004, 43, 2334−2375. (d) Long, J. R.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1213−1214 themed issue on metal−organic frameworks. (e) Janiak, C.; Vieth, J. K. New J. Chem. 2010, 34, 2366−2388. (f) Zhou, H. C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673− 674 2012 Metal−Organic Frameworks special issue. (g) Wang, C.; Lin, W. J. Am. Chem. Soc. 2013, 135, 13222−13234. (h) Zhou, H. C. J.; Kitagawa, S. Chem. Soc. Rev. 2014, 43, 5415−5418 themed issue on metal−organic frameworks. (2) (a) Zhao, D.; Timmons, D. J.; Yuan, D.; Zhou, H.-C. Acc. Chem. Res. 2011, 44, 123−133. (b) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, C.-M. Chem. Rev. 2012, 112, 1001−1033. (c) Song, L.; Zhang, J.; Sun, L.; Xu, F.; Li, F.; Zhang, H.; Si, X.; Jiao, C.; Li, Z.; Liu, S.; Liu, Y.; Zhou, H.; Sun, D.; Du, Y.; Cao, Z.; Gabelica, Z. Energy Environ. Sci. 2012, 5, 7508−7520. (d) Cook, T. R.; Zheng, Y.-R.; Stang, P. J. Chem. Rev. 2013, 113, 734−777. (e) Du, M.; Li, C. P.; Liu, C. S.; Fang, S. M. Coord. Chem. Rev. 2013, 257, 1282−1305. (f) Zhao, X. L.; Sun, W. Y. CrystEngComm 2014, 16, 3247−3258. (g) He, Y.; Li, B.; O’Keeffe, M.; Chen, B. Chem. Soc. Rev. 2014, 43, 5618−5656. (h) Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Park, J.; Park, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gentle, T., III; Bosch, M.; Zhou, H.-C. Chem. Soc. Rev. 2014, 43, 5561−5593. (3) (a) Wood, T. E.; Thompson, A. Chem. Rev. 2007, 107, 1831− 1861. (b) Maeda, H. Eur. J. Org. Chem. 2007, 5313−5325. (c) Baudron, S. A. CrystEngComm 2010, 12, 2288−2295. (d) Baudron, S. A. Dalton Trans. 2013, 42, 7498−7509. (4) (a) Simard, M.; Su, D.; Wuest, J. D. J. Am. Chem. Soc. 1991, 113, 4696−4698. (b) Mann, S. Nature 1993, 365, 499−505. (c) Hosseini, M. W. Acc. Chem. Res. 2005, 38, 313−323. (d) Hosseini, M. W. Chem. Commun. 2005, 5825−5829. (5) (a) Kitagawa, S.; Noro, S.; Nakamura, T. Chem. Commun. 2006, 701−707. (b) Andruh, M. Chem. Commun. 2007, 2565−2577. (c) Garibay, S. J.; Stork, J. R.; Cohen, S. M. Prog. Inorg. Chem. 2009, 56, 335−378. (d) Burrows, A. D. CrystEngComm 2011, 13, 3623−3642. (e) Das, M. C.; Xiang, S.; Zhang, Z.; Chen, B. Angew. Chem., Int. Ed. 2011, 50, 10510−10520. (f) Kumar, G.; Gupta, R. Chem. Soc. Rev. 2013, 24, 9403−9453. (6) (a) Halper, S. R.; Cohen, S. M. Inorg. Chem. 2005, 44, 486−488. (b) Murphy, D. L.; Malachowski, M. R.; Campana, C. F.; Cohen, S. M. Chem. Commun. 2005, 5506−5508. (c) Halper, S. R.; Do, L.; Stork, J. R.; Cohen, S. M. J. Am. Chem. Soc. 2006, 128, 15255−15268. (d) Stork, J. R.; Thoi, V. S.; Cohen, S. M. Inorg. Chem. 2007, 46, 11213−11223. (e) Garibay, S.; Stork, J. R.; Wang, Z.; Cohen, S. M.; Telfer, S. G. Chem. Commun. 2007, 4881−4883. (7) (a) Salazar-Mendoza, D.; Baudron, S. A.; Hosseini, M. W. Chem. Commun. 2007, 2252−2254. (b) Salazar-Mendoza, D.; Baudron, S. A.; Hosseini, M. W. Inorg. Chem. 2008, 47, 766−768. (c) Pogozhev, D.; Baudron, S. A.; Hosseini, M. W. Inorg. Chem. 2010, 49, 331−338. (d) Kilduff, B.; Pogozhev, D.; Baudron, S. A.; Hosseini, M. W. Inorg. Chem. 2010, 49, 11231−11239. (e) Béziau, A.; Baudron, S. A.; Hosseini, M. W. Dalton Trans. 2012, 41, 7227−7234. (f) Ruffin, R.; Baudron, S. A.; Salazar-Mendoza, D.; Hosseini, M. W. Chem.Eur. J. 2014, 20, 2449−2453. G

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry (g) Zhou, L.; Xue, Y. S.; Xu, Y.; Zhang, J.; Du, H.−B. CrystEngComm 2013, 15, 7315−7320. (16) (a) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem. Rev. 2003, 246, 247−289. (b) Leong, W. L.; Vittal, J. J. Chem. Rev. 2011, 111, 688−764. (c) Alexandrov, E. V.; Blatov, V. A.; Proserpio, D. M. Acta Crystallogr. 2012, A68, 484−493. (d) Yang, G.-P.; Hou, L.; Luan, X.-J.; Wu, B.; Wang, Y.-Y. Chem. Soc. Rev. 2012, 41, 6992−7000. (e) Jiang, H.-L.; Makal, T. A.; Zhou, H.-C. Coord. Chem. Rev. 2013, 257, 2232−2249. (17) Spek, A. L. PLATON; The University of Utrecht: Utrecht, The Netherlands, 1999. (18) (a) De Munno, G.; Julve, M.; Lloret, F.; Derory, A. J. Chem. Soc., Dalton Trans. 1993, 1179−1184. (b) Colacio, E.; Lloret, F.; Navarrete, M.; Romerosa, A.; Stoeckli-Evans, H.; Suarez-Valera, J. New J. Chem. 2005, 29, 1189−1194. (c) Alborés, P.; Rentschler, E. Dalton Trans. 2010, 39, 5005−5019. (d) Thuéry, P. Inorg. Chem. 2013, 52, 435−447. (19) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112−122.

H

DOI: 10.1021/ic502950k Inorg. Chem. XXXX, XXX, XXX−XXX