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Dysprosium Heteroleptic Corrole-Phthalocyanine Triple-Decker Complexes: Synthesis, Crystal Structure, and Electrochemical and Magnetic Properties Guifen Lu,*,† Cheng He,† Kang Wang,‡ Junshan Sun,§ Dongdong Qi,‡ Lei Gong,‡ Chiming Wang,‡ Zhongping Ou,† Sen Yan,† Suyuan Zeng,∥ and Weihua Zhu*,† †

School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People’s Republic of China Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, People’s Republic of China § College of Chemistry and Chemical Engineering, TaiShan University, Taian 271000, People’s Republic of China ∥ School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People’s Republic of China ‡

S Supporting Information *

ABSTRACT: Two triple-decker dinuclear sandwich dysprosium complexes, which are represented as Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) and Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2), were synthesized and characterized by spectroscopic and electrochemical methods in nonaqueous media. Their electronic structures were also investigated on the basis of TD-DFT calculations. The sandwich triple-decker nature with the molecular conformation of [Pc(OC5H11)8]Dy[Cor(FPh)3]Dy[Pc(OC5H11)8] for compound 1 was unambiguously revealed by single-crystal X-ray diffraction analysis and showed each dyprosium ion to be octacoordinated by the isoindole and pyrrole nitrogen atoms of an outer phthalocyanine ring and the central corrole ring, respectively. In addition, the magnetic properties of both compounds have also been characterized for exploring the functionalities of these types of triple-decker complexes.

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their unique optical and magnetic properties.11−14,22,27−30 However, there have been no examples of dysprosium corroles reported to date. This is unsurprising because the efficient synthetic methodologies for corroles were just reported 18 years ago by groups of Paolesse, Gross, and Gryko.31−34 Different from phthalocyanines and porphyrins, corroles are ring-contracted 18-π-electron tetrapyrrolic macrocycles, which contain a direct carbon−carbon bond between two pyrrole rings and act as trianionic ligands because of three NH protons in the inner core. The special structure gives corroles exhibit unique physicochemical properties, which render them extensively applicable to the areas of catalysis, sensors, nonlinear optical materials, and medicinal chemistry.35−46 Despite this, the “periodic table of corrole complexes” is not as rich as that of porphyrins or phthalocyanines. Until now, there are only 42 kinds of elements that can be coordinated with corrole ligands.47 Particularly, corrole complexes with rareearth-metal ions are extremely rare. The first example of lanthanide corrole complexes (of La, Gd, and Tb), which shows their potential use as fluorescence imaging agents, was reported by Arnold et al. in 2013.48 In recent years, we have successfully synthesized several rare-earth corrole-phthalocyanine heteroleptic triple-decker complexes M2Pc*2Cor* (M = Y, Pr, Nd,

INTRODUCTION Extensive work has been done in the preparation and characterization of sandwich multidecker tetrapyrrole rareearth complexes, which have remarkable optical, electrical, and electrochemical properties that stem from their inter-ring π−π interactions and rare-earth ionic f−f interactions.1−4 Homoleptic multitetrapyrrole or the mixed-(phthalocyaninato)(porphyrinato)lanthanide multidecker (e.g., double-, triple-, and quadruple-decker) complexes are known.5−9 Among them, dysprosium derivatives have flourished prominently in recent years and studied using not only spectroscopic and electrochemical methods but also magnetic susceptibility measurements,10−22 because they have a variety of applications in the area of molecular devices, particularly as single-molecule magnets (SMMs) or single-ion magnets (SIMs), due to their large ground-state spin and intrinsic magnetic anisotropy.4,23−25 Changing different π-conjugated macrocyclic ligands is one of the effective synthetic strategies for tuning the optical, electrical, and magnetic properties of sandwich multidecker tetrapyrrole rare-earth complexes.3 This is also true for dysprosium derivatives. In 2013, Jiang et al. extended tetrapyrrole-based dysprosium sandwich complexes to the mixed phthalocyaninato-Schiff base double- and quadrupledecker species.26 Since then, numerous sandwich dysprosium systems simultaneously containing tetrapyrrole derivatives or mixed with other π-conjugated macrocyclic organic molecules (e.g., Schiff base, calix[4]arene, etc.) have been explored for © 2017 American Chemical Society

Received: April 26, 2017 Published: September 13, 2017 11503

DOI: 10.1021/acs.inorgchem.7b01060 Inorg. Chem. 2017, 56, 11503−11512

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Inorganic Chemistry

PBE1PBE functional was used to calculate electronic absorption spectra of Dy2[Pc(OC5H11)8]2[Cor(FPh)3]. The TD-DFT calculations were carried out by using a mixed basis set (the 6-31G(d) basis set for C/H/O/N/F and the SDDALL effective core basis for Dy). All calculations were carried out by using the Gaussian 09 (Revision D.01) and TD-Analy 1.13 software. Synthesis Procedure. The investigated compounds 1 and 2 were synthesized according to published procedures.49−52 Preparation of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1). First, a mixture of Dy(acac)3·nH2O (48 mg, ca. 0.1 mmol) and H2[Pc(OC5H11)8] (120 mg, 0.1 mmol) in DMF (3 mL) was heated at 140 °C under nitrogen for 1 h, yielding the “half-sandwich” compound Dy[Pc(OC5H11)8](acac). The resulting blue solution was cooled to room temperature, and the solvent was evaporated under reduced pressure. This was then added to H3[Cor(FPh)3] (58 mg, 0.1 mmol) which was dissolved in noctanol (4 mL) and heated to 170 °C for 2 h in the presence of 1,8diazabicyclo[5.4.0]undec-7-ene (DBU; 20 mg, 0.13 mmol) under a slow stream of nitrogen. After being cooled to room temperature, the solvent was removed under vacuum and the residue was purified by column chromatography on silica gel with CHCl3 as eluent. A small amount of unreacted H3[Cor(FPh)3] and the homoleptic bis(phthalocyaninato) dysprosium(III) complex Dy[Pc(OC5H11)8]2 were collected as the first and second fractions, respectively. The target mixed ring triple-decker product was obtained as the third fraction. Repeated chromatography followed by recrystallization from CHCl3 and CH3OH gave pure Dy2[Pc(OC5H11)8]2[Cor(FPh)3] as gray-green microcrystals. Yield: ca. 14 mg (10%); MALDI-TOF mass: calcd 3305.740, found 3306.686. Anal. Calcd for Dy2C181H212N20O16F3, (CH3OH): C, 65.49; H, 6.52; N, 8.39. Found: C, 65.31; H, 6.43; N, 8.45. Preparation of Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2). Complex 2 was prepared in a manner analogous to that used to prepare 1, except that H3[Cor(ClPh)3] (63 mg, 0.1 mmol) was used instead of H3[Cor(FPh)3]. Yield: ca. 12 mg (8%). MALDI-TOF mass: calcd 3355.103, found 3356.037. Anal. Calcd for Dy2C181H212N20O16Cl3·CH3OH: C, 64.54; H, 6.43; N, 8.27. Found: C, 64.73; H, 6.74; N, 7.90. Crystal Data for Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1). Single crystals of compound 1 suitable for X-ray diffraction analysis were obtained by diffusion of methanol into a solution of the corresponding compound in chloroform. CCDC 1524773 for 1, containing supplementary crystallographic data for this paper, can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif.

Sm, Eu, Gd, Tb), which exhibit potential applications in the area of molecular-based information storage devices.49−52 In the present work, we synthesized two dysprosium heteroleptic corrole-phthalocyanine triple-decker complexes, Dy 2 [Pc(OC 5 H 1 1 ) 8 ] 2 [Cor(FPh) 3 ], (1) and Dy 2 [Pc(OC5H11)8]2[Cor(ClPh)3] (2), where Pc = phthalocyanine and Cor = corrole (Chart 1). Both of them were characterized Chart 1. Structures of Dysprosium Heteroleptic CorrolePhthalocyanine Triple-Decker Complexes, Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) and Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2)

for their spectroscopic and electrochemical properties, and the structure of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) was confirmed by single-crystal X-ray diffraction analysis. In addition, the magnetic properties of each compound have been fully characterized to explore the functionalities of these types of triple-decker complexes.

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EXPERIMENTAL SECTION

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General Information. n-Octanol was distilled from sodium under reduced pressure prior to use. Absolute dichloromethane (CH2Cl2, 99.8%, EMD Chemicals Inc.) was used for electrochemistry without further purification. Tetra-n-butylammonium perchlorate (TBAP), used as a supporting electrolyte, was purchased from Sigma-Aldrich, recrystallized from ethyl alcohol, and dried under vacuum at 40 °C for at least 1 week prior to use. All other reagents and solvents were purchased from Sinopharm Chemical Reagent Co. or Aldrich Chemical Co. and used as received. The compounds H2[Pc(OC5H11)8],20,53 Dy(acac)3·nH2O,54 H3[Cor(FPh)3], and H3[Cor(ClPh)3]55 were prepared according to the literature methods. Measurements. IR spectra (KBr pellets) were recorded on an AVATAR-370 spectrometer. Electronic absorption spectra were recorded on a Hitachi U-4100 spectrophotometer. MALDI-TOF mass spectra were carried out on a Bruker BIFLEX III ultrahighresolution instrument. Elemental analyses were performed on a FLASH1112A Element analyzer. Cyclic voltammetry was carried out at 298 K using a CHI-730C Electrochemical Workstation. Crystallographic measurements were carried out using a Rigaku Saturn 724+ CCD X-ray diffractometer by using monochromated Mo Kα radiation (λ = 0.71070 Å) at 120 K. Magnetic measurements were performed on a Quantum Design MPMS XL-5 SQUID magnetometer on multicrystalline samples. Data were corrected for the diamagnetism of the samples using Pascal’s constants and for the sample holder by measurement. X-ray photoelectron spectroscopy (XPS) was carried out on a PHI 5300 ESCA System (PerkineElmer, USA). The timedependent density functional theory (TD-DFT) method of the hybrid

RESULTS AND DISCUSSION Synthesis. According to our previously described procedure,49−52 the target complexes 1 and 2 were obtained by prior generation of the “half-sandwich” phthalocyanine complex Dy[Pc(OC5H11)8](acac) from H2[Pc(OC5H11)8]20,53 and Dy(acac)3·nH2O54 in refluxing DMF, followed by treatment with the corresponding free-base corrole H3[Cor(FPh)3] or H3[Cor(ClPh)3]55 in n-octanol containing DBU at reflux and purified by repeated chromatography with CHCl3 as eluent. The yields for both complexes (10% for 1 and 8% for 2) were lower than those for their analogous complexes Eu2[Pc(R)8]2[Cor(ClPh)3] (15−16% for R = H, OC5H11, OC8H17),51,52 Eu2[Pc(OC4H9)8]2[Cor(Ph)n(NO2Ph)3−n] (40−54% for n = 0−3),49 and M2[Pc(OC4H9)8]2[Cor(ClPh)3] (16−31% for M = Pr−Tb, except Pm)50 by using the same method but higher than that of Y2[Pc(OC5H11)8]2[Cor(ClPh)3] (1%). Apparently, the size of the central metal has an effect on the yield of these compounds. Such an effect also exists for rare-earth double- or triple-decker phthalocyanine/porphyrin complexes.56−58 After repeated column chromatography and recrystallization, satisfactory elemental analysis results were obtained for both of the newly prepared dysprosium heteroleptic corrole-phthalocyanine triple-decker complexes 1 and 2, which have good 11504

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M2[Pc(OC5H11)8]2[Cor(ClPh)3] (M = Y, Dy, Eu) in CH2Cl2 were calculated, and the values of E in eV are summarized in Table S2 in the Supporting Information. It is noteworthy that there is a linear correlation between the energy (E) of the main Q band of compounds M2[Pc(OC5H11)8]2[Cor(ClPh)3] (M = Y, Dy, Eu) in CH2Cl2 versus the ionic radii of lanthanide for these complexes with two identical metals, as shown in Figure 2. A similar trend is also observed for other rare-earth tripledecker species.50,61−63

solubility in common organic solvents such as CHCl3, CH2Cl2, and toluene. These two triple-decker complexes were also characterized by MALDI-TOF mass spectra, which clearly showed intense signals for the protonated molecular ion [M + H]+ for 1 and 2, as shown in Figures S1 and S2 in the Supporting Information, respectively. These results unambiguously confirmed the identity of these compounds. Unfortunately, satisfactory 1H NMR data could not be obtained due to the interactions between the unpaired electron and the highly paramagnetic characteristic of the dysprosium ions. Electronic Absorption Spectra. The electronic absorption spectra of compounds 1 and 2 were recorded in CH2Cl2, and the data are summarized in Table S1 in the Supporting Information, which also includes data for the earlier reported Eu(III) and Y(III) derivatives50,51 and the radius of the rareearth ion of each compound.59 Figure 1 shows their electronic

Figure 2. Correlation between the energy for the main Q band of M2[Pc(OC5H11)8]2[Cor(ClPh)3] as a function of ionic radius of MIII (M = Y, Dy, Eu) in CH2Cl2.

Electronic Structures. In order to gain insights into the electronic absorption spectra of rare-earth heteroleptic corrolephthalocyanine triple-decker complexes, the time-dependent density functional theory (TD-DFT)64 method of the hybrid PBE1PBE65 functional was carried out by using the Gaussian 09 D.01 program66 and TD-Analy 1.13.67 The experimental and simulated electronic absorption spectra for Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) in CH2Cl2 are shown in Figure 3, and molecular orbital energy and electronic transitions of 1

Figure 1. Electronic absorption spectra of triple-decker complexs 1 (a) and 2 (b) in CH2Cl2.

absorption spectra in the range of 250−1000 nm, which shows the typical features observed in the electronic absorption spectra of rare-earth heteroleptic triple-decker corrole-phthalocyanine complexes. The N band of phthalocyanine is observed at 295 nm for compounds 1 and 2.60 The Soret bands appear at 351 and 419−422 nm, while the Q bands for these compounds are observed at 675 nm with one weak band in the range 538−540 nm. In addition, there is one weak Q band at ∼806 nm. These wavelengths are very similar to published wavelengths of analogous triple-decker sandwich complexes.49−52 Interestingly, the position of the relatively intense Q-band strongly depends on the interspacing between the two macrocycles: i.e., the size of the central metal ion.50,61−63 For instance, the position of this band is at 675 nm for compound 2 in CH2Cl2 but at 678 and 674 nm for Eu2[Pc(OC5H11)8]2[Cor(ClPh)3] and Y2[Pc(OC5H11)8]2[Cor(ClPh)3], respectively, in the same solution. It is blue-shifted by 3 nm for 2 in comparison to the analogous Eu2[Pc(OC5H11)8]2[Cor(ClPh)3] derivative but red-shifted by 1 nm in comparison to Y2[Pc(OC5H11)8]2[Cor(ClPh)3], in accordance with the order of the ionic radius of the central metals. The energies (E) of the main Q band of compounds

Figure 3. Experimental and simulated electronic absorption spectra for Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) in CH2Cl2.

as a typical example are shown in Figure 4. A mixed basis set, which is a combination of the 6-31G(d) basis set68 for C/H/ O/N/F and the SDDALL effective core basis set69 for Dy was chosen. Tables S3 and S4 in the Supporting Information also show the time-dependent density functional theory (TD-DFT) calculation results of compound 1 and the important electron transitions. 11505

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contrast, the electron density movement is also mainly from the Pc rings to the Cor ring. In summary, the binding of Pc and Cor rings induces an interesting result that the excited electron always jumps between Pc and Cor rings. The whole UV−vis spectrum can be attributed as this type of electron jumping, including the Cor → Pc jumping for 490−850 nm and Pc → Cor for 400−490 nm. IR Spectra. IR spectroscopy has been proven to be a useful tool to reveal the nature of the phthalocyaninato ligands.1,70−73 For octakis(alkyloxy)-substituted phthalocyanine in rare-earth sandwich complexes, two medium-intensity absorptions at 1310−1320 and 1377 cm−1 are assigned to the IR marker bands of phthalocyanine monoanion radical. However, reduction of the phthalocyanine monoanion radical causes the appearance phthalocyanine dianion IR marker bands at 1381 cm−1 as a strong signal and 1311 cm−1 as a very weak signal.1 Figures S3 and S4 in the Supporting Information display the IR spectra of complexes 1 and 2 in the region of 400−4000 cm−1, respectively. Due to the similarity of their molecular structures to those of the previously reported M2[Pc(OC4H9)8]2[Cor(ClPh)3] derivatives (where M = Pr−Tb except Pm),50 complexes 1 and 2 show similar IR characteristics. Observation of an intense absorption at 1381 cm−1 together with a very weak band at 1312 cm−1 well defines the characteristics of the dianionic nature of phthalocyanine in complexes 1 and 2. In addition, two intense absorptions at ca. 1047 and 1274 cm−1 are assigned to the symmetric and asymmetric C−O−C stretching and three intense absorption bands in the region from 2853 to 2958 cm−1 are typical C−H stretching vibrations of the CH3 and CH2 groups of the octyloxy side chains.71,72 Crystal Structure. The mixed tetrapyrrole nature with sandwich triple-decker molecular structure for Dy 2[Pc(OC5H11)8]2[Cor(FPh)3] (1) was clearly revealed by singlecrystal X-ray diffraction analysis, as shown in Figure 5. The compound crystallizes in the triclinic system with a P1̅ space group. The crystallographic data and selected bond lengths and angles are given in Table 1 and Table S5 in the Supporting Information, respectively. It is worth noting that structurally characterized corroles with rare-earth-metal ions are limited to the monometallic derivatives (Mes2(p-OMePh)Cor)M (M = La·4.5DME, Tb·4DME, Gd·TACNMe3)48 and the europium corrole-phthalocyanine heteroleptic triple-decker complexes Eu 2 [Pc(OC 4 H 9 ) 8 ] 2 [Cor(Ph)(NO 2 Ph) 2 49 and Eu 2 [Pc(R)8]2[Cor(ClPh)3] (R = OC4H9, OC8H17).50,51 It also represents the first dysprosium heteroleptic corrole-phthalocyanine triple-decker complex to have been structurally characterized. As can be seen in Figure 5, each dyprosium ion is octacoordinated by isoindole and pyrrole nitrogen atoms of the phthalocyanine ring and the central corrole ring, confirming the ligand arrangement of [Pc(OC5H11)8]Dy[Cor(FPh)3]Dy[Pc(OC5H11)8] in the triple-decker molecules. However, the two dyprosium ions are not identical in terms of their coordination geometry, and they adopt a slightly distorted square prismatic geometry with twist angles of 16.1° for Dy1 and 11.2° for Dy2, respectively. Both dyprosium ions lie closer to the phthalocyanine ring due to its larger central cavity in comparison with the corrole ring (1.285 vs 1.767 Å for Dy1 and 1.304 vs 1.752 Å for Dy2). Thus, the average Dy1− N[Pc(OC5H11)8] bond length (2.335 Å) is significantly shorter than the average Dy1−N[Cor(FPh)3] distance (2.541 Å). The

Figure 4. Molecular orbital energy and electronic transitions of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1), calculated at the PBE1PBE level.

As can be found, the absorption bands of region I (from 750 to 850 nm) are attributed to the electron transitions from HOMO-2(α) to LUMO+1(α), HOMO(α) to LUMO+3(α)/ LUMO+4(α), HOMO-2(β) to LUMO+3(β), and HOMO(β) to LUMO(β)/LUMO+1(β)/LUMO+4(β). The total electron density movement is mainly from the Cor ring to the Pc rings. In addition, this absorbing region is a newly generated peak induced by the binding between Pc and Cor rings. The absorption bands of region II (from 585 to 750 nm) are attributed to the electron transitions from HOMO-2(α) to LUMO+1(α)/LUMO+2(α), HOMO(α) to LUMO+3(α)/ LUMO+4(α), HOMO-3(β) to LUMO(β), HOMO-2(β) to LUMO+2(β)/LUMO+3(β), and HOMO(β) to LUMO+4(β). The electron density movement is mainly from the Cor ring to the double Pc rings together with the peripheral conjugated system to the 18-π-electron conjugated cores of the Pc rings. The absorption bands of region III (from 490 to 585 nm) are attributed to the electron transitions from HOMO-24(α)/ HOMO-17(α)/HOMO-15(α)/HOMO-14(α)/HOMO-13(α) to LUMO(α), HOMO-1(α) to LUMO+5(α), and HOMO -3(β) to LUMO+1(β), Similarly, the electron density movement is also mainly from the Cor ring to the double Pc rings. The absorption bands of region IV (from 400 to 490 nm) are attributed to the electron transitions from HOMO-32(α)/ HOMO-24(α)/HOMO-23(α)/HOMO-20(α)/HOMO17(α)/HOMO-14(α)/HOMO-13(α) to LUMO(α), HOMO1(α) to LUMO+5(α), and HOMO-1(β) to LUMO+5(β). In 11506

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Electrochemical Properties. The electrochemical behavior of the newly synthesized triple-decker complexes 1 and 2 was investigated by cyclic voltammetry (CV) in CH2Cl2 containing 0.1 M TBAP. Cyclic voltammograms are shown in Figure 6, and the measured half-wave potentials are given in Table 2. As detailed in Figure 6, both of the complexes exhibit five reversible or quasi-reversible one-electron oxidations at 1.40−1.41, 1.25−1.27, 0.99−1.00, 0.69−0.70, and 0.27−0.28 V, together with three reductions at −0.10 to −0.13, −1.26 to −1.29, and −1.51 to −1.48 V, within the potential window of CH2Cl2. It is worth noting that X-ray photoelectron spectroscopy (XPS) was employed to characterize the valence state of two dysprosium ions in the investigated complexes. As can be seen in Figure S5 in the Supporting Information, two peaks due to Dy 3d3/2 and Dy 3d5/2 were observed at 1334.4 and 1296.6 eV for 1 and at 1334.4 and 1296.5 eV for 2, indicating the existence of Dy3+ in both triple-decker complexes.74,75 However, DyIII is redox-inactive; thus, these redox processes are due to successive removal or addition of electrons from or to the ligand-based orbitals. As seen in Table 2, the first oxidation and first reduction of compound 2 are slightly shifted to the positive direction in comparison with those of compound 1, due to the electron-withdrawing effect of a Cl atom being stronger than that of an F atom. Therefore, compound 2 is harder to oxidize and easier to reduce than compound 1. For comparison, the potentials measured under the same solution conditions for Eu2[Pc(OC5H11)8]2[Cor(ClPh)3]51 and Y2[Pc(OC5H11)8]2[Cor(ClPh)3],50 which have structures similar to that of compound 2, are also given in Table 2. As shown in Figure S6 in the Supporting Information, the redox potentials of M2[Pc(OC5H11)8]2[Cor(ClPh)3] (M = Y, Dy, Eu) are linearly related to the ionic radius of the central ions, indicating the presence of π−π interactions in these heteroleptic sandwich derivatives. In addition, the differences in E1/2 values between the first oxidation and first reduction of complexes 1 and 2 are 0.40 and 0.38 V, respectively, which accord well with known data for Eu2[Pc(R)8]2[Cor(ClPh)3] and M2[Pc(OC4H9)8]2[Cor(ClPh)3], where R = OC5H11, OC8H17 and M = Pr, Nd, Sm, Eu, Gd, Tb.50−52 Both currently examined triple-decker complexes showed the same potential difference (ΔE1/2 = 1.16 V) between the first and second reductions, which is also similar to that of the known analogues. Magnetic Properties. The magnetic properties of 1 and 2 were studied as a preliminary trial toward exploring the functionalities of these novel heteroleptic corrole-phthalocyanine lanthanide triple-decker complexes. As can be seen in Figure 7, the curves of the magnetic susceptibility χmT for compounds 1 and 2 show a temperature-dependent character in the temperature range from 2 to 300 K under an applied field of 1000 Oe. The χmT values of 31.68 and 26.04 cm3 K mol−1 for 1 and 2 at 300 K are consistent with the value of 28.72 cm3 K mol−1 for two dysprosium(III) ions (6H15/2, S = 5/2, L = 5, g = 4/3) and one radical.4,11,23,28−30,76 When the temperature is lowered, the χmT values of both compounds decrease slowly until about 50 K and then decrease to minimum values of 19.56 and 20.75 cm3 K mol−1 for 1 and 2 at 2 K, respectively, owing to the crystal field effect for both compounds and possible intramolecular antiferromagnetic dipole−dipole interactions.11,12 In addition, as shown in Figure S7 in the Supporting Information, the M versus H curves for both compounds 1 and 2 display a rapid increase at low field and eventually achieve the maximum values of 9.14 and 8.13 μB for 1 and 2, respectively, which is far from the theoretical magnetization saturation value

Figure 5. Molecular structure of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) in (a) top view and (b) side view, with all hydrogen atoms omitted for clarity. Color scheme: Dy, pink; N, blue; C, black; O, red; F, green.

Table 1. Crystal Data and Structure Refinement of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) formula formula wt cryst syst space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) Z V (Å3) abs coeff (mm−1) θ range (deg) F000 R1 (I > 2θ)a wR2 (I > 2θ)b Rint (all) wR2 (all) GOF on F2 a

C181H212F3Dy2N20O16 3305.71 triclinic P1̅ 18.181(4) 20.424(4) 24.026(5) 102.69(3) 102.04(3) 99.22(3) 2 8312(3) 0.964 3 to 25 3450 0.1302 0.4371 0.1605 0.4371 1.214

R1 = ∑||Fo| − |Fc||/∑|Fo|. bwR2 = [∑w(Fo2 − Fc2)2/∑w(Fo2)2]1/2.

Dy2−N[Pc(OC5H11)8] bond length (2.326 Å) is also shorter than that of Dy2−N[Cor(FPh)3] (2.531 Å). These structural features are similar to those of earlier reported rare-earth tripledecker tetrapyrrole compounds. The metal−metal distance between the two dyprosium atoms is 3.519 Å in compound 1, which is slightly shorter than those between the two europium atoms in Eu2[Pc(OC4H9)8]2[Cor(ClPh)3] (3.586 Å),50 Eu2[Pc(OC 8 H 17 ) 8 ] 2 [Cor(ClPh) 3 ] (3.574 Å), 51 and Eu 2 [Pc(OC4H9)8]2[Cor(Ph)(NO2Ph)2] (3.578 Å),49 probably because of the lanthanoid ion contraction. 11507

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Figure 6. Cyclic voltammograms of (a) Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) and (b) Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2) in CH2Cl2 containing 0.1 M TBAP.

Table 2. Half-Wave Potentials (E1/2, V vs SCE) of Complexes 1 and 2 and M2[Pc(OC5H11)8]2[Cor(ClPh)3] (M = Y, Eu) in CH2Cl2 with 0.1 M TBAP oxidation

reduction

compound

Oxd5

Oxd4

Oxd3

Oxd2

Oxd1

Red1

Red2

Red3

E1/2(Ox1Red1)

E1/2(Red1Red2)

ref

Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2) Eu2[Pc(OC5H11)8]2[Cor(ClPh)3] Y2[Pc(OC5H11)8]2[Cor(ClPh)3]

1.40 1.41 1.39 1.43

1.25 1.27 1.25 1.27

0.99 1.00 1.05 0.99

0.69 0.70 0.70 0.70

0.27 0.28 0.33 0.27

−0.13 −0.10 −0.08 −0.12

−1.29 −1.26 −1.27 −1.29

−1.51 −1.48 −1.45 −1.50

0.40 0.38 0.41 0.39

1.16 1.16 1.19 1.17

this work this work 51 50

Figure 7. Temperature (T) dependence of χmT for powder samples of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1) (a) and Dy2[Pc(OC5H11)8]2[Cor(ClPh)3] (2) (b) at 1000 Oe.

of 20.00 μB for two dysprosium ions (10 μB for each Dy(III) ion). The result also indicates the presence of crystal field effects and thus leads to magnetic anisotropy for the Dy(III) ion in these triple-decker complexes. This is also true for other dysprosium mixed tetrapyrrole double-, triple-, or multipledecker complexes.4 The measurement of alternating-current (ac) magnetic susceptibility of both compounds was carried out in a 3.0 Oe ac field oscillating in the range of 1−660 Hz. Figure 8 shows the plots of χ′ vs T and χ″ vs T in a 0 direct current (dc) magnetic field for compounds 1 and 2. As can be seen, compound 2 exhibits frequency-dependent character in the in-phase signal (χ′) and out-of-phase signal (χ″), indicating the slow relaxation of magnetization and revealing the SMM nature of this complex. However, in the case of 1, only very inconspicuous frequency-dependent character in the out-of-phase signal (χ″) could be observed. These results reveal the influence of the substituent at the meso-attached phenyl moieties of the corrole ligand on the magnetic properties. Unfortunately, a further understanding of the corresponding relaxation process for both

compounds failed, since no complex shows χ″ peaks due to the fast relaxation associated with the quantum tunneling of magnetization (QTM) even under 2000 Oe dc magnetic field (Figure S8 in the Supporting Information). In comparison to the dysprosium phthalocyaninate tripledeckers Dy2(obPc)3 (obPc = dianion of 2,3,9,10,16,17,23,24octabutoxy-phthalocyanine),77,78 compounds 1 and 2 possess more significant QTM, which is related to the coordination geometry of the Dy ions. It has been demonstrated that the degree of suppression of the QTM in the sandwich-type tetrapyrrole dysprosium SMMs was revealed to increase along with a decrease in the deviation of the twist angle from 45°. In the case of Dy2[Pc(OC5H11)8]2[Cor(FPh)3] (1), twist angles for the Dy(III) ions are 15.8 and 10.7°, significantly deviating from 45°, which resulted in the observation of the fast relaxation ascribed to QTM under the 0 and even 2000 Oe direct current magnetic field. In contrast, the twist angle for the Dy ions in Dy2(obPc)3 is 32°, leading to the suppression of the QTM under 2000 Oe direct current magnetic field with a maximum χ″mT peak observed at 4.5 K at a frequency of 1488 11508

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Figure 8. Temperature dependence of the in-phase (χ′) and out-of-phase (χ″) ac susceptibility of 1 (a, b) and 2 (c, d), respectively, under 0 applied dc field.

Hz.77,78 In addition, the curves of χmT for compounds 1 and 2 revealed possible intramolecular antiferromagnetic interactions between the two Dy3+ ions. This is different from the case for Dy2(obPc)3 but similar to that for (thd)2DyPcDy(thd)2 (thd = 2,2,6,6-tetramethylheptane-3,5-dionato),79 suggesting that the Dy3+ ions in 1 and 2 present an easy-plane magnetic anisotropy, which may also be responsible for the significant QTM.

Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Corresponding Authors

*E-mail for G.L.: [email protected]. *E-mail for W.Z.: [email protected].

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ORCID

CONCLUSIONS In summary, two novel dysprosium heteroleptic triple-decker corrole-phthalocyanine complexes have been prepared and characterized by spectroscopic and electrochemical methods, representing the first investigated Dy-corrole complexes, which further enrich the “periodic table of corrole complexes”. The sandwich triple-decker nature of these compounds was unambiguously revealed on the basis of a single-crystal X-ray diffraction analysis of [Pc(OC5H11)8]Dy[Cor(FPh)3]Dy[Pc(OC5H11)8] (1). Investigation into the magnetic properties of both dysprosium complexes revealed their SMM nature. Further efforts toward synthesizing heteroleptic corrolephthalocyanine lanthanide triple-decker complexes with A2Bcorroles and exploring their functionalities are in progress.

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AUTHOR INFORMATION

Guifen Lu: 0000-0002-3374-4140 Suyuan Zeng: 0000-0002-6421-8565 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support was obtained from the National Natural Science Foundation of China (Grant Nos. 21001054, 21401009, and 21171076) and Foundation of Jiangsu University (FCJJ2015020).

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REFERENCES

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01060. MALDI-TOF mass spectra, IR spectra, high-resolution Dy 3d XPS spectra, light-induced electron transferring direction (LIETD, isovalue 5.0 × 10−4 e au−3), lightharvesting efficiency (LHE), information on α/β orbitals, electronic absorption spectral data, selected bond distances and angles for Dy2[Pc(OC5H11)8]2[Cor(FPh)3], and M vs H/T curves at 2.0 K ac susceptibility in a dc field of 2000 Oe (PDF) Accession Codes

CCDC 1524773 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge 11509

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DOI: 10.1021/acs.inorgchem.7b01060 Inorg. Chem. 2017, 56, 11503−11512