A New Type of Three-Dimensional Hybrid Polymeric Haloplumbate

Oct 2, 2018 - The interconnection of rare high-nuclear heterometallic clusters and one-dimensional haloplumbate [Pb2X9] chains gives a new type of ...
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Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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A New Type of Three-Dimensional Hybrid Polymeric Haloplumbate Based on Rare High-Nuclear Heterometallic Clusters Jian Zhou,*,† Hong Xiao,† Hua-Hong Zou,*,‡ and Xing Liu† †

Chongqing Key Laboratory of Inorganic Functional Materials, College of Chemistry, Chongqing Normal University, Chongqing, 401331, P.R. China ‡ State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry & Pharmacy of Guangxi Normal University, Guilin, 541004, P.R. China

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S Supporting Information *

ABSTRACT: A series of new three-dimensional hybrid heterometallic haloplumbates [Pb8M(μ3-O)2X8(XH)(eg)3]n {H2eg = ethylene glycol; X = Cl, M = Co (1a), Ni (1b), Zn (1c); X = Br, M = Ni (2a), Zn (2b); X = I, M = Zn (3)} have been solvothermally synthesized and structurally characterized. Compounds 1a−c, 2a−b, and 3 consist of one-dimensional haloplumbate [Pb2X9] chains, and heptanuclear heterometallic [Pb6M(μ3-O)2(eg)3] clusters based on two [Pb3(μ3O)(eg)1.5] cores share one M2+ ion, which are interconnected to generate three-dimensional heterometallic frameworks. Although a few heterometallic haloplumbates incorporating other metal complexes have been reported, they usually exhibit low-dimensional structures. The present heterometallic haloplumbates offer good examples of applying high-nuclear heterometallic [Pb6MO2(eg)3] clusters to construct a new type of high-dimensional hybrid heterometallic haloplumbate. Compounds 1a−b and 2a indicate unusual ferrimagnetic behavior. Their optical properties are investigated at room temperature, and density functional theory calculations of compounds 1c, 2b, and 3 are also studied.

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INTRODUCTION Crystalline hybrid haloplumbates have been widely fueled by their diverse topological structures associated with excellent chemical−physical properties in semiconductor, photocatalysis, luminescence, nonlinear optics, thermochromism, and the others.1 A large number of hybrid haloplumbates have been made by a great diversity of organic structure-directing agents with different sizes, shapes, and charges, which might be a great influence on the structural construction of hybrid haloplumbates.1,2 Their new properties unobserved in inorganic haloplumbates could result from either a new structural type or the functional hybridization between inorganic and organic components. Recently, metal complexes (MCs) instead of organic structure-directing agents have been applied successfully for the haloplumbate reaction system, thus leading to a wide variety of unusual hybrid haloplumbates combined with metal complexes, including [Ln(L)8]3+ (Ln = lanthanide metal ion, L = DMF or DMSO)3 and [M(L)x]n+ (M = transition metal ion, L = chelating ligands).4 The reported MCs are generally low-nuclear and consist of only one type of metal ion. However, the extended hybrid haloplumbates based on heterometallic clusters as structure-directing agents are very scarce, and the only example is two-dimensional (2D) heterometallic bromoplumbate [CdPb6Br6(eg)4]n (H2eg = ethylene glycol) with luminescence properties recently reported by our group,5 whose heterometallic [Cd(Pb4O4)Br2] crown cluster is pentanuclear. Therefore, it is still a large © XXXX American Chemical Society

challenging goal to synthesize hybrid extended heterometallic haloplumbates with higher-nuclear heterometallic clusters, mainly because they might show the unique properties of integrated higher-nuclear heterometallic clusters with host inorganic haloplumbate frameworks, which offer great possibilities to build hybrid multifunctional materials. High-nuclear heterometallic clusters are often considered to show better performances than those built up from single metal ions, mainly because the coexistence of different metal ions in the same cluster skeleton might enrich their structural diversities with the addition of new properties.6 So far, a number of high-nuclear p/d, d/d, and d/f heterometallic clusters based on the linkages of different metal ions and various N/O-based bridging organic ligands have been synthesized by the solvo-(or hydro-)thermal route,6,7 and the typical examples are [Cu6Ln2] (Ln = Gd, Dy),7a [Ag9Znx] (x = 2, 4),7b [Cu12Zn8],7c MnIII16M4 (M = Ca, Sr),7d [Fe18Ln6] (Ln = Dy, Gd, Tb, Ho, Sm, Eu, Y),7e [Ti10Ln8] (Ln = Eu, Sm, Gd),7f [Ti4Eu5],7g [MnSb4],7h and [Mn13Cd6],7c which can be further connected by organic bridging ligands to generate the extended hybrid architectures associated with important photocatalysis, magnetic, and luminescent properties. If highnuclear heterometallic clusters acting as structure-directing agents incorporate into the varied inorganic haloplumbate Received: July 22, 2018

A

DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 1. Crystallographic Data for All Compounds 1a

1b

1c

formula fw crystal system space group a, Å b, Å c, Å β, deg V, Å3 Z T, K calcd density, Mg·m−3 F(000) 2θ (max), deg total reflns collected unique reflns no. of param R1 [I > 2σ(I)] wR2 (all data) GOF on F2

C6H13Cl9CoO8Pb8 2248.77 monoclinic P2/n 9.373(6) 8.786(7) 17.617(12) 91.465(17) 1450.3(18) 2 293(2) 5.101 1896 55.86 39586 3479 147 0.0294 0.0764 1.099 2a

C6H13Cl9NiO8Pb8 2248.53 monoclinic P2/n 9.3129(3) 8.8140(4) 17.5791(7) 91.6680(10) 1442.35(10) 2 293(2) 5.138 1898 50.18 29626 2571 147 0.0329 0.0909 1.042 2b

C6H13Cl9O8Pb8Zn 2255.22 monoclinic P2/n 9.3764(19) 8.7849(18) 17.638(4) 91.55(3) 1452.3(5) 2 293(2) 5.155 1902 55.94 31559 3472 147 0.0467 0.1237 1.017 3

formula fw crystal system space group a, Å b, Å c, Å β, deg V, 3 Z T, K calcd density, Mg·m−3 F(000) 2θ (max), deg total reflns collected unique reflns no. of param R1 [I > 2σ(I)] wR2 (all data) GOF on F2

C6H13Br9NiO8Pb8 2648.59 monoclinic P2/n 9.5860(2) 9.2297(2) 17.9769(4) 92.497(2) 1589.01(6) 2 293(2) 5.534 2222 50.04 5438 2796 146 0.0305 0.0625 1.006

C6H13Br9O8Pb8Zn 2655.28 monoclinic P2/n 9.624(9) 9.161(9) 17.993(7) 92.52(2) 1585(2) 2 293(2) 5.562 2226 50.20 31696 2812 146 0.0227 0.0535 1.067

C6H13I9O8Pb8Zn 3078.28 monoclinic P2/n 10.0281(5) 9.7742(5) 18.5026(10) 93.8961(18) 1809.37(16) 2 296(2) 5.648 2550 55.90 65040 4347 147 0.0336 0.0836 1.076

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framework, new types of hybrid heterometallic haloplumbates with useful properties could be expected. Directed by this idea, we initiated the exploration of the synthetic system Pb2+/X−/ M2+/H2eg (X = Cl, Br, I; M = Co, Ni, Zn) with the goal of achieving hybrid heterometallic haloplumbates incorporating high-nuclear heterometallic clusters and successfully obtained a series of new three-dimensional (3D) heterometallic haloplumbates Pb8M(μ3-O)2X8(XH)(eg)3]n {H2eg = ethylene glycol; X = Cl, M = Co (1a), Ni (1b), Zn (1c); X = Br, M = Ni (2a), Zn (2b); X = I, M = Zn (3)}, which offer the only examples of 3D hybrid heterometallic haloplumbates incorporating the highest-nuclear heterometallic [Pb6M(μ3-O)2(eg)3] clusters, because the number of metal ions in a single heterometallic cluster is not more than five within any known haloplumbates.3−5

EXPERIMENTAL SECTION

Materials and Methods. Ethylene glycol solvent and other reagents were of analytical reagent grade and used without any further purification. Elemental analyses of C and H were performed with a PE2400 II elemental analyzer. Fourier transform infrared (FT-IR) spectra were carried out on a Nicolet Magna-IR 550 spectrometer (400−4000 cm−1). The UV/vis spectra were measured with a PE Lambda 900 UV/vis spectrophotometer. Powder XRD patterns are carried out on the angular range of 2θ = 5−50° on a Bruker D8 advance diffractometer using CuKα radiation (Figure S1). Photoluminescence spectra of compounds 1c, 2b, and 3 were recorded at room temperature with a modular double-grating excitation spectrofluorimeter with a TRIAX 320 emission monochromator. All magnetization of compounds 1a−b and 2a were obtained with a Quantum Design MPMS-XL-5 magnetometer. The band structures and density of states (DOS) of compounds 1c, 2b, and 3 were theoretically calculated by CASTEP. Syntheses of [Pb8M(μ3-O)2Cl8(ClH)(eg)3]n {M = Co (1a), Ni (1b), Zn (1c)}. Pb(NO3)2 (0.0527 g), NaCl (0.0374 g), MAc2·4H2O {CoAc2·4H2O (0.0564 g) for 1a, NiAc2·4H2O (0.0437 g) for 1b, and B

DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 1. (a) The asymmetric unit of 1a with the labeling scheme (all H atoms are omitted for clarity), (b) complex [Co(eg)3]4− anion, showing distorted [CoO6] trigonal prism, (c) heptanuclear heterometallic [Pb6Co(μ3-O)2(eg)3] cluster containing heterometallic [CoPb3O4] cubane, (d− g) the coordination environments of Pb2+ ions [symmetry operation: (i) 1 − x, 1 − y, 1 − z; (ii) −1 + x, −1 + y, z; (iii) 1 − x, −y, 1 − z; (iv) x, −1 + y, z; (v) 0.5 − x, y, 0.5 − z; (vi) −1 + x, y, z; (vii) 2 − x, 1 − y, 1 − z; the dotted lines indicate weak Pb···Cl interactions], (h) 1D [Pb2Cl9] chain.

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ZnAc2·4H2O (0.0436 g) for 1c}, and ethylene glycol (1 mL) were placed in a thick Pyrex tube (ca. 20 cm long). The sealed tubes were kept at 160 °C for 8 days to yield red-block crystals of 1a (35% yield based on Pb(NO3)2), green-block crystals of 1b (75% yield based on Pb(NO3)2), and colorless-block crystals of 1c (69% yield based on Pb(NO3)2), respectively. Anal. Calcd for 1a (C6H13Cl9CoO8Pb8): C, 3.20; H, 0.58. Found: C, 3.31; H, 0.64. Anal. Calcd for 1b (C6H13Cl9NiO8Pb8): C, 3.21; H, 0.58. Found: C, 3.29; H, 0.65. Anal. Calcd for 1c (C6H13Cl9O8Pb8Zn): C, 3.20; H, 0.58. Found: C, 3.28; H, 0.64. Syntheses of [Pb8M(μ3-O)2Br8(BrH)(eg)3]n {M = Ni (2a), Zn (2b)}. Pb(NO3)2 (0.0289 g), KBr (0.0155 g), MAc2·4H2O {NiAc2·4H2O (0.0143 g for 2a and ZnAc2·4H2O (0.0197 g for 2b}, and ethylene glycol (1 mL) were placed in a thick Pyrex tube (ca. 20 cm long) were placed in a thick Pyrex tube (ca. 20 cm long). The sealed tubes were kept at 160 °C for 5 days to obtain yellow-block crystals of 2a (78% yield based on Pb(NO3)2), and colorless-block crystals of 2b (75% yield based on Pb(NO3)2), respectively. Anal. Calcd for 2a (C6H13Br9NiO8Pb8): C, 2.72; H, 0.49. Found: C, 2.81; H, 0.55. Anal. Calcd for 2b (C6H13Br9O8Pb8Zn): C, 2.71; H, 0.49. Found: C, 2.78; H, 0.54. Synthesis of [Pb8Zn(μ3-O)2I8(IH)(eg)3]n (3). Pb(NO3)2 (0.0167 g), KI (0.0284 g), ZnAc2·4H2O (0.0155 g) for 3, and ethylene glycol (1 mL) were placed in a thick Pyrex tube (ca. 20 cm long). The sealed tubes were kept at 160 °C for 6 days to yield yellow crystals of 3 (57% yield based on Pb(NO3)2). Anal. Calcd for 3 (C6H13I9O8Pb8Zn): C, 2.34; H, 0.43. Found: C, 2.40; H, 0.49. X-ray Crystallography. Intensity data of all compounds were collected on a Rigaku Mercury CCD diffractometer by a ω-scan method with graphite monochromated Mo Kα radiation (λ = 0.71073). Absorption corrections were made by the multiscan technique. Their structures were solved by Direct Methods (SHELXS-97)8 and refined by the SHELXL-97 program.9 Non-H atoms were refined with anisotropic displacement parameters, while the H atoms bonded on C atoms were positioned with idealized geometry. Relevant crystal data can be listed in Table 1. The CCDC numbers of all compounds are 1857139−1857144.

RESULTS AND DISCUSSION Syntheses of Hybrid Heterometallic Haloplumbates. MCs as structure-directing agents have been widely regarded as a viable approach for the preparation of metal haloplumbates under hydro-(or solvo-)thermal conditions, and the organic components of MCs mainly including traditional aliphatic chelating organic amines and aromatic πconjugated ligands are preferable to chelate metal ions to easily form saturated mononuclear MCs, but high-nuclear heterometallic clusters are very scarce, because the saturated MCs cannot further bridge other metal ions.3,4 By contrast, aliphatic chelating alcohols is rarely used to construct MCs acting as new structure-directing agents within the metal haloplumbates.5,10 Ethylene glycol is one of excellent aliphatic chelating alcohols, and it is selected as an aliphatic chelating/bridging ligand, a series of new 3-D heterometallic haloplumbates [Pb8M(μ3-O)2X8(XH)(eg)3]n {H2eg = ethylene glycol; X = Cl, M = Co (1a), Ni (1b), Zn (1c); X = Br, M = Ni (2a), Zn (2b); X = I, M = Zn (3)} were successfully made, and each M2+ ion is chelated by three deprotonated eg2− ligands to produce a trigonal prism [M(eg)3]4− ion, whose alkoxo groups are further bound to the Pb2+ ion, resulting in unsaturated high-nuclear heterometallic [Pb6M(μ3-O)2(eg)3] clusters. Such unsaturated heterometallic clusters can be further integrated into haloplumbate frameworks to form new hybrid heterometallic haloplumbates, which provide the only examples of 3D hybrid heterometallic haloplumbates based on high-nuclear heterometallic [Pb6M(μ3-O)2(eg)3] clusters. Crystal Structures. All Compounds are isomorphism and crystallize in the monoclinic space group P2/n. So the structure of 1a will be only discussed. The asymmetric unit of 1a consists of four Pb2+ ions, one and a half eg2− ligands, one O atom, four Cl− anions, half of -Cl−H group, and half of Co2+ ion (both the -Cl−H group and Co2+ ion are seated at the special location with 2-fold symmetry, Figure 1a). It is C

DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 2. (a) The unsaturated [Pb6M(μ3-O)2(eg)3] cluster linking with four Cl− anions, (b−c) 2D layers constructed by the combination of both [Pb6M(μ3-O)2(eg)3] clusters and 1D [Pb2Cl9]n chains, (d) 3D framework of 1a. All H atoms are omitted for clarity.

manner, and linked with the [Pb6Co(μ3-O)2(eg)3] clusters via Pb3−Cl1 bonds to form a 2D layer (Figure 2b). The similar [Pb2Cl9]n chains and [Pb6Co(μ3-O)2(eg)3] clusters are interconnected via Pb2−Cl2 bonds to give another 2D layer (Figure 2c). The combination of two types of 2D layers suffices to form a 3D network structure (Figure 2d). Notably, the reported unsaturated MCs acting as either decorating groups or bridging groups can connect directly to the haloplumbate skeletal core, resulting in low-dimensional structures;3a,4a,e−h for instance, the discrete {[Co(2,2′-bipy)]3Pb7Br24}4− anion was constructed by the cyclic [Pb7Br24] unit attached via three decorating groups [Co(2,2′-bipy)]2+,4h the 1D neutral chain {Pb3I12[Cu(phen)2]2}n is built up from a 1D iodoplumbate chain [[PbCuII5]n decorated by unsaturated complex [CuII(phen)2]2+,4a and the 2D layer {[Nd2(DMF)12(in)2](Pb8I20)}n (Hin = isonicotinic acid) was constructed by the linkages of 1D chains [Pb8I20]n and binuclear neodymium complexes [Nd2(DMF)12(in)2]4+.3a However, 3D heterometallic haloplumbates based on unsaturated MCs have not been observed to the best of our knowledge. Therefore, compounds 1a−c, 2a−d, and 3a−b provide the only examples of 3D heterometallic haloplumbates based on the unsaturated high-nuclear [Pb6M(μ3-O)2(eg)3] clusters acting as bridging groups. So far, a lot of the [Pb4O4] cubane-based solid materials with photoluminescent and nonlinear-optical properties have been reported,10c,13 but the heterometallic cubanes containing lead and other metal elements are relatively scarce, and the unique example is heptanuclear [Pb6Ni(μ3-O)8] cluster based on corner-fused double [Pb3Ni(μ3-O)4] cubanes,14 which is further connected by deprotonated 4,6-dinitro-5-hydroxyisophthalic acid spacers to form the 3D framework. Notably, similar [Pb6 M(μ3-O) 8] clusters decorated by aliphatic chelating alcohols have not be observed to date. Therefore, compounds 1a−c, 2a−b, and 3 offer a new type of [Pb6M(μ3-

assumed that the normal valences of Co, Pb, Cl, and O are +2, + 2, −1 and −2, respectively, and the charge of eg2− ligand is −2, the charge of the [Pb8Co(μ3-O)2X9(eg)3] framework stoichiometry is −1, which must be balanced by one additional H atoms. This H atom should be attached to the Cl3 atom, because the occupancy rates of Co1 and Cl3 atoms are 0.5, and those of other atoms are 1. The 3D frameworks of 1a are constructed by the combination of heptanuclear heterometallic [Pb6Co(μ3-O)2(eg)3] clusters and 1D [Pb2Cl9]n chains. The heptanuclear [Pb6Co(μ3-O)2(eg)3] cluster (Figure 1c) can be regarded as corner-fused double cubanes, where two [CoPb3(μ3-O)4] distorted cubanes share one Co2+ ion. The eg2− ligand shows chelating/bridging coordination modes, and each alkoxo group links with one Co2+ ion and two Pb2+ ions. The Pb(4)2+ ion lies in a holodirected hexa-coordinate environment defined by six Cl− ions, while other Pb2+ ions adopt hemidirected geometries with the hypothesized lone pair of electrons as stereochemically active. The Pb−O bond distances are in the range of 2.269(6)−2.513(6), and Pb−Cl bond lengths vary from 2.791(3) to 3.038(3), compared with corresponding values in other compounds.4c,11 The Pb(1/2/ 3)2+ ions also have weak Pb···Cl interactions (3.166−3.713),12 which are slightly shorter than the sum of the van der Waals’ radii (4.15), leading to another holodirected geometry (Figure 1d−g). The Co2+ ion is coordinated by six O atoms from three eg2− ligands to form a distorted trigonal prism with the Co−O bond lengths varying from 2.078(6) to 2.104(6) (Figure 2b). Two [PbCl6] units are interconnected by edge-sharing Cl− anions to give dimeric [Pb2Cl10] unit with Pb···Pb distance of 4.696(2), which is further joined together by corner-sharing Cl− anions, resulting in a 1D [Pb2Cl9]n chain. The unsaturated [Pb6Co(μ3-O)2(eg)3] cluster has four coordination sites at four Pb2+ ions (Figure 2a), where each cluster is connected to four 1D [Pb2Cl9]n chains via four Pb− Cl bonds. The [Pb2Cl9]n chains are aligned in a parallel D

DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 3. (a) Absorption spectra of all compounds at room temperature, (b) emission spectra of compounds 1c, 2b, and 3 at room temperature.

Figure 4. (a) The total DOS and partial DOS of 1c. (b) The band structures of 1c. The Fermi level is set at 0 eV.

to-metal (Zn2+/Pb2+) charge transition and Zn2+/Pb2+centered transitions. Evidently, the emission peak of compounds 1c, 2b, and 3 shows a red shift in the series Cl → Br → I, mainly because different X− ions have a significant effect on luminescent emission. Theoretical Studies. To further investigate the origin of the luminescent emissions of compounds 1c, 2b and 3, their electronic band structures are calculated by CASTEP (Figure 4 and Figure S3). Considering that the contributions of H and C atoms in the vicinity of the Fermi level are very small, their contributions can be almost ignored. The contribution of the X-p state near the Fermi level is slightly larger than that of O 2p states, and similar phenomena are also found in other lead oxyhalides17 or bismuth oxyhalides.18 The top of the valence band (VB) is mainly composed of O-2p and X-p states with small portions of Pb-6s and Zn-3d states, while the bottom of the conduction band (CB) is derived mainly from the Pb-6p state with small amounts of Zn-4s state. Therefore, the origin of the luminescent emissions of compounds 1c, 2b, and 3 can be attributed to the combination of ligand-to-metal charge transition (LMCT) and metal-to-metal charge transition (MMCT). The LMCT can be transferred from the occupied O-2p and X-p orbitals to the unoccupied Zn-4s and Pb-6p orbitals. The MMCT can be composed of Zn2+ and Pb2+ centered transitions. One can be transferred from the occupied Zn-3d orbital to the unoccupied Zn-4s orbital, and the other can be transferred from the occupied Pb-6s orbital to the unoccupied Pb-6p orbital. The band structures of compounds 1c, 2b, and 3 show the direct band gaps of 3.10, 2.88, and 2.56 eV, respectively, which are very close to the experimental values. Clearly, the change of band gaps of compounds 1c, 2b, and 3 decreases with increasing atomic number of halogen elements, which might be closely related to the more dramatic effect of halogen on the band gap of haloplumbates.

O)2(eg)3] cluster decorated by ethylene glycols. Moreover, no heptanuclear heterometallic [Pb6M(μ3-O)8] cubanes are further linked by inorgainc haloplumbate units to generate various extended frameworks. Hence, compounds 1a−c, 2a−b, and 3 represent the only examples of 3D heterometallic haloplumbate frameworks based on the linkages of new heterometallic [Pb6M(μ3-O)2(eg)3] cubanes and inorgainc haloplumbate [Pb2X9]n chains. Optical Properties. The IR spectra of compounds 2a−d and 3a−b exhibit weak characteristic stretching vibration of the -Br−H group at 2663 cm−1 and the -I−H group at 2360 cm−1, respectively, but the stretching vibration of the -Cl−H group and the stretching bands of −CH2 group in compounds 1a−c are overlapped at 2809−2860 cm−1 (Figure S2). These -X−H stretching vibrations can be compared with the corresponding values of the reported -X−H groups (2800−2900 cm−1 for ν−Cl−H, 2500−2700 cm−1 for ν−Br−H and 2200−2400 cm−1 for ν−I−H).15 The strong bands at 1020−1040 cm−1 can be characteristic of the -C−O stretching. UV/vis absorption spectra of all compounds at room temperature are shown in Figure 3a. The optical band gaps are 2.88 eV for 1a, 3.86 eV for 1b, 3.05 eV for 1c, 3.31 eV for 2a, 2.98 eV for 2b, and 2.47 eV for 3, suggesting that compounds 1a−c, 2a−b, and 3 have the potential wide-band gap semiconductor properties. Moreover, some significant absorptions in 1a {2.39 eV (519 nm)}, 1b {1.77 eV (700 nm) and 3.17 eV (391 nm)}, and 2a {1.80 eV (689 nm) and 3.22 eV (385 nm)} can arise from the d−d transitions in [Co(eg)3] or [Ni(eg)3] complex cores of [Pb6M(μ3-O)2(eg)3] clusters, and the similar d−d transition is also observed in other Co2+/Ni2+ complexes.16 The luminescent properties of compounds 1c, 2b, and 3 at room temperature were shown in Figure 3b. Upon excitation at 398 nm, compounds 1c, 2b, and 3 exhibit the strong wide emissions at 541, 568, and 647 nm, respectively, which could be tentatively assigned to the combination of X−/eg2− ligandE

DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 5. Temperature dependence of the χMT curve for compounds 1a (a), 1b (b), and 2a (c). Temperature dependence of the ac susceptibilities below 12 K (1a, d), 20 K (1b, e), and 20 K (2a, f); plots of χMT vs T in a sequence of ZFC (red), and FC (black) at a field of 20 Oe for 1a (g), 1b (h), and 2a (i).

Magnetic Properties. The direct-current magnetization measurements were performed on polycrystalline samples of compounds 1a−b and 2a between 2 and 300 K under an external field of 1000 Oe (Figure 5a−c). For 1a, the observed value of χMT at 300 K is 1.85 cm3·mol−1·K, and slightly smaller than the value (1.875 cm3·mol−1·K) for one magnetically isolated high-spin Co(II) ion (S = 3/2, g = 2.0). Mainly due to their strong spin−orbital coupling interactions in the Co(II) ion system.19 On decreasing the temperature, the χMT value slowly increases until ∼25 K, and then rapidly and abruptly increases to reach a maximum of 7.79 cm3·mol−1·K at 6.9 K, followed by a sudden drop to 3.3 cm3·mol−1·K at 2 K. For 1b and 2a, the χMT values at 300 K are 1.83 and 1.67 cm3·mol−1· K, respectively. These are higher than the value (1 cm3·mol−1· K) for an isolated high-spin Ni(II) ion (S = 1, g = 2.0). On cooling, the χMT values slowly increase until ∼50 K (1b) and ∼25 K (2a), and then quickly increase to reach a maximum of 15.95 and 13.86 cm3·mol−1·K at 13.5 K (1b) and 13.2 K (2a), respectively, and then quickly drop down to 4.26 (1b) and 3.09 cm3·mol−1·K (2a) at 2 K. This indicates obviously magnetic anisotropy in the system. The magnetic interactions of M2+ (M = Co, Ni) in adjacent chains and layers should be negligible because the chains and layers are well-separated by the Pb2+ ions with distances longer than 8.7 in all complexes. In order to shed light on this configuration, we also performed temperature dependence of susceptibility measurements in the AC mode for these complexes. Figure 5d−f shows the dispersion in the real part of the χ′ and in the imaginary part χ″versus T plots at

frequencies ranging from 1 to 997 Hz with an amplitude of 2.5 Oe. The real part of the AC susceptibility shows the existence of sharp and rather rounded peaks at different temperatures, which have no frequency dependence. In the thermal profile for these complexes in ZFC−FC cycles, a similar discrepancy between the ZFC and FC values was observed (Figure 5g−i). From the divergent point of the FC and ZFC measurements, the TN value was obtained. Compounds 1a−b and 2a might show a ferrimagnetic interaction below TN K, leading to a 3D ferrimagnetic long-range ordering.20

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CONCLUSION Although a few heterometallic haloplumbates built up from the linkages of inorganic Pb/X units and MCs have been reported, their MCs are usually low-nuclear and only contain one type of metal ion. Compounds 1a−c, 2a−b, and 3 provide a new type of 3D hybrid heterometallic haloplumbate constructed by the linkages of high-nuclear heterometallic [Pb6M(μ3-O)2(eg)3] clusters and 1D haloplumbate [Pb2X9] chains. The unique properties of MCs have been successfully integrated with host inorganic haloplumbate frameworks, resulting in the formation of hybrid multifunctional haloplumbates, namely, ferrimagnetic semiconductors for compounds 1a−b and 2a, and luminescent semiconductors for compounds 1c, 2b, and 3. This work not only enriches the structural type of hybrid haloplumbates, but also offers a new way to prepare novel multifunctional haloplumbates based on other high-nuclear heterometallic clusters. F

DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX

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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.8b02069. IR spectra, XRD data, and density of states and electronic band structures of both 2b and 3 (PDF) Accession Codes

CCDC 1857139−1857144 contain 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 [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*(J.Z.) E-mail: [email protected]. *(H.-H.Z.) E-mail:[email protected]. ORCID

Jian Zhou: 0000-0002-8290-8893 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the NNSF of China (Nos. 21671029 and 21601038), the NSF of Chongqing municipality (Nos. cstc2015jcyjBX0117 and cstc2018jcyjAX0157), Program for Leading Talents of Scientific and Technological Innovation in Chongqing municipality (No. CSTCCXLJRC201707), and Program for Excellent Talents in Chongqing Higher Education Institutions. The authors are also grateful to Chongqing Normal University for financial support (Nos. 14CSLJ02 and 13XLZ07).

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REFERENCES

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DOI: 10.1021/acs.inorgchem.8b02069 Inorg. Chem. XXXX, XXX, XXX−XXX