Structural Diversity and Magnetic Properties of Seven Coordination

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Structural Diversity and Magnetic Properties of Seven Coordination Polymers Based on 2,2'-Phosphinico-dibenzoate Ligand Zhao-Xi Wang, Lin-Fei Wu, Hong-Ping Xiao, Xing-Hua Luo, and Ming-Xing Li Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00747 • Publication Date (Web): 04 Aug 2016 Downloaded from http://pubs.acs.org on August 8, 2016

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Crystal Growth & Design

Structural Diversity and Magnetic Properties of Seven Coordination Polymers Based on 2,2'-Phosphinico-dibenzoate Ligand Zhao-Xi Wang,*,†,‡ Lin-Fei Wu,† Hong-Ping Xiao,*,§ Xing-Hua Luo,† Ming-Xing Li *,† †

Department of Chemistry, Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University, Shanghai 200444, People’s Republic of China

‡

State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People’s Republic of China § College of Chemistry & Material Engineering, Wenzhou University, Wenzhou 325035, People’s Republic of China * Corresponding author. E-mail: [email protected]; [email protected]; [email protected] RECEIVED DATE

Abstract: Seven novel coordination polymers based on 2,2'-phosphinico-dibenzoic acid (H3L), namely {[Zn3L2(H2O)4]·2H2O}n (1), [Zn3L2(4,4'-bipy)2]n (2), [Zn(HL)(2,2'-bipy)(H2O)]n (3), {[Cd9L6(H2O)8]·4H2O}n (4), [Cd8L4(OH)2(OAc)2(4,4'-bipy)]n (5), [Mn3L2(4,4'-bipy)(EtOH) (H2O)2]n (6), and [Mn(HL)(2,2'-bipy)(H2O)]n (7), were synthesized under hydro(solvo)thermal conditions. These compounds crystallize in the triclinic Pī space group for 1, 4, 5 and 6, monoclinic space group C2/c for 2, and monoclinic P21/c space group for 3 and 7. The L3– ligand displays versatile binding modes in 1−7. Compound 1 is a 1-D chain coordination polymer with 3-D supramolecular framework. Compound 2 is a 3-D porous MOF with two different 4,4'-bipyridine linkers. Compound 3 and 7 show 1-D zigzag chain structures. Compound 4 exhibits a sophisticated 3-D MOF constructed from two types of Cd8 clusters and one Cd2 dimer, which is the first example exhibiting the coexistence of four coordination modes of L3− ligands and four geometries of Cd(II) ions in one network. Compound 5 displays a 2-D network containing ring-like Cd8 cluster. Compound 6 shows a 2-D layered network with 4,4'-bipyridine linker. Their luminescence and variable-temperature magnetic property were investigated, which indicated ligand-centered emission in 1−5 and weak antiferromagnetic coupling between Mn(II) ions in 6 and 7. . INTRODUCTION Coordination polymers (CPs) and metal-organic frameworks (MOFs) formed by linking metal ions through multifunctional ligands are attracting wide attention,1-6 owing to their great potential in gas adsorption, catalysis, ion exchange, molecular magnet, luminescence, sensor as well as their beautiful architecture.7-13 In controlling the structural feature of coordination polymer, organic linker and coordination geometry adopted by metal ion are two primary factors.14-16 Polycarboxylic acids are a sort of very important organic linkers, which have been widely used to construct CPs and MOFs.17-19 Among the reported significant works based on V-shaped semi-rigid polycarboxylate ligands,20-22 a series of bifunctional carboxyphosphinate ligands remains largely unexplored.23-25 Metal phosphonates are a class of important organic–inorganic hybrid materials with beautiful architectures as well as interesting physical properties, such as sorption, catalysis, optical properties and magnetism.26-29 Although many fruitful works have been reported on phosphonate compounds, the compounds based on phosphinic acid derived from phosphonic acid have rarely been investigated.30,31 2,2'-Phosphinico-dibenzoic acid (H3L) is a V-shaped

semi-rigid carboxyphosphinate ligand, which was synthesized by Segall et al forty years ago.32 Nevertheless, only two coordination compounds [Ag(H2L)]n and [Ag3(L)]n involving H3L have been reported by us up to date.33 As a good candidate of building block for construction of coordination polymers, H3L exhibits several interesting characteristics: (i) It can be partially or completely deprotonated to generate H2L–, HL2–, and L3– anions by controlling pH value carefully, which allows the anion ligands to display various coordination modes (Scheme 1). (ii) Contribution to its two carboxylate groups and one phosphinate unit, these multifunctional coordination sites provide a high likelihood for construction of multi-dimensional frameworks. (iii) It is easily to form a chiral center with different coordination modes based on four groups around the phosphorus atom.33 Among many strategies to construct coordination polymers, the self-assembly of metal ion and polycarboxylate cooperating with N-donor ligand is one of the most effective approaches.34-37 Several well-known MOFs were prepared by N-donor ligands such as 2,4,6-tri(4-pyridyl)-1,3,5- triazine (tpt) (CMP-33, 34, 35) and N,N′,N′′-tri(4-pyridyl)-1,3,5-benzene-tricarboxamide (tpbtc) (CMP-37) with carboxylic acids.38-40 It is well

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known that bipyridine derivatives such as 4,4'-bipyridine (4,4'-bipy) and 2,2'-bipyridine (2,2'-bipy) are multifunctional ligands largely used in the assembly of CPs.41,42 They act as bridging or chelating ligands to connect metal ions to form coordination compounds with established properties.43,44 This prompted us to add auxiliary N-donor ligands 4,4'-bipy and 2,2'-bipy in the reaction mixture to construct coordination polymers. In this work, we utilized 2,2'-phosphinico-dibenzoic acid as primary ligand and two N-donor ligands as auxiliary ligand, successfully prepared seven coordination polymers with diverse structures and physical properties. It is interesting that the carboxyphosphinate anion displays four types of coordination modes and the Cd(II) ion exhibit four kinds of geometries in {[Cd9L6(H2O)8]·4H2O}n (4) compound.

Scheme 1. Coordination modes of 2,2'-phosphinico-dibenzoate. EXPERIMENTAL SECTION Materials and Methods. All reagents and solvents employed in the present work were of analytical grade as obtained from commercial sources without further purification. The ligand 2,2'-phosphinico-dibenzoic acid was synthesized according to the literature method.32, 45,46 Elemental analyses for C, H and N were performed on a Vario EL-III elemental analyzer. The FT-IR spectra were recorded using KBr pellets in the range from 4000 to 400 cm−1 on a Nicolet Avatar A370 spectrophotometer. Powder X-ray diffraction (PXRD) data were collected on a DX-2700 diffractometer with Cu Kα radiation (λ = 1.5406 Å) over the 2θ range of 5−30° at room temperature to check the phase purity of bulk materials. Thermogravimetric analyses (TGA) were performed on a Netzsch STA 449C thermal analyzer at a heating rate of 10 °C min–1 in air. Luminescence spectra of the solid samples were recorded on a Shimadzu RF-5301 spectrophotometer. Magnetic susceptibilities were measured on a Quantum Design MPMS-XL7 SQUID

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magnetometer in a field of 1 kOe. Diamagnetic corrections were made with Pascal’s constants. Synthesis of {[Zn3L2(H2O)4]·2H2O}n (1). A mixture of ZnCl2·H2O (0.2 mmol), H3L (0.1 mmol), triethylamine (38 µL) and H2O (6 ml) was sealed in a 15 ml Teflon-lined stainless steel autoclave and heated at 120 ºC for 3 days, and then cooled to room temperature at a rate of 10 ºC·h−1. Colorless prism crystals of 1 were obtained in 71% yield based on H3L. Anal. Calcd for Zn3C28H26O18P2 (908.54): C, 37.01; H, 2.88. Found: C, 36.59; H, 2.48%. IR (KBr, cm−1): 3375(s), 3064(w), 1621(s), 1577(s), 1544(s), 1489(m), 1448(m), 1420(s), 1140(s), 1084(s), 1046(m), 1031(m), 879(m), 847(m), 802(m), 748(s), 717(m), 664(m), 587(m). Synthesis of [Zn3L2(4,4'-bipy)2]n (2). A mixture of Zn(OAc)2·2H2O (0.3 mmol), H3L (0.15 mmol), 4,4'-bipy (0.15 mmol), H2O (7 ml) and EtOH (1 ml) were sealed in a 15 ml Teflon-lined stainless steel autoclave and heated at 180 ºC for 3 days, and then cooled to room temperature at a rate of 10 ºC·h−1. Colorless prism crystals of 2 were obtained in 59% yield based on H3L. Anal. Calcd for Zn3C48H32N4O12P2 (1114.96): C, 51.71; H, 2.89; N, 5.02. Found: C, 51.07; H, 2.45; N, 5.31%. IR (KBr, cm−1): 3406(s), 3094(w), 1599(s), 1580(s), 1556(s), 1391(m), 1334(m), 1133(s), 1073(s), 995(s), 761(s), 744(m), 707(m), 655(m), 574(m), 558(m). Synthesis of [Zn(HL)(2,2'-bipy)(H2O)]n (3). The synthetic method of 3 is similar to that of 2, only 2,2'-bipy instead of 4,4'-bipy. Colorless prism crystals of 3 were obtained in 78% yield based on H3L. Anal. Calcd for ZnC24H19N2O7P (543.75): C, 53.01; H, 3.52, N, 5.15. Found: C, 53.21; H, 4.05, N, 5.01%. IR (KBr, cm−1): 3403(s), 3085(w), 2731(w), 1714(s), 1605(s), 1568(s), 1555(s), 1473(m), 1443(m), 1400(s), 1301(m), 1254(m), 1171(s), 1138(s), 1121(m), 1014(m), 767(s), 736(m), 704(m), 561(s). Synthesis of {[Cd9L6(H2O)8]·4H2O}n (4). A mixture of CdBr2 (0.5 mmol), H3L (0.25 mmol), H2O (3 ml) and DMA (1 ml) was placed in Teflon-lined stainless steel autoclave and heated to 85 ºC for 3 days, and then cooled to room temperature at a rate of 10 ºC·h−1. Colorless prism crystals of 4 were obtained in 82% yield based on H3L. Anal. Calcd for Cd9C84H74O48P6 (3046.84): C, 32.92; H, 2.43. Found: C, 33.64; H, 2.49%. IR (KBr, cm−1): 3454(s), 3056(w), 16010(s), 1575(s), 1555(s), 1171(s), 1157(s), 1129(s), 1065(m), 1011(m), 814(m), 755(s). Synthesis of [Cd8L4(OH)2(OAc)2(4,4'-bipy)]n (5). A mixture of Cd(OAc)2·2H2O (0.225 mmol), H3L (0.04 mmol), 4,4'-bipy (0.055 mmol), H2O (6 ml) and EtOH (2 ml) was placed in Teflon-lined stainless steel autoclave and heated to 140 ºC for 3 days, and then cooled to room temperature at a rate of 10 ºC·h−1. Colorless block crystals of 5 were obtained in 58% yield based on H3L. Anal. Calcd for Cd8C70H48N2O30P4 (2420.18): C, 34.74; H, 2.00, N,


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1.16. Found: C, 34.05; H, 2.08, N, 1.28%. IR (KBr, cm−1): 3423(s), 3054(w), 1605(s), 1571(s), 1549(s), 1403(s), 1161(s), 1148(s), 1133(s), 1079(m), 1011(m), 808(m), 759(s), 567(s), 539(m). Synthesis of [Mn3L2(4,4'-bipy)(EtOH)(H2O)2]n (6). A mixture of Mn(OAc)2·4H2O (0.2 mmol), H3L (0.1 mmol), 4,4'-bipy (0.05 mmol), H2O (4 ml) and EtOH (1 ml) was placed in Teflon-lined stainless steel autoclave and heated to 160 ºC for 3 days, and then cooled to room temperature at a rate of 10 ºC·h−1. Colorless block crystals of 6 were obtained in 54% yield based on H3L. Anal. Calcd for Mn3C42H44N2O18P2 (1091.56): C, 46.21; H, 4.06, N, 2.56. Found: C, 46.85; H, 4.44, N, 2.04%. IR (KBr, cm−1): 3441(s), 3054(w), 1600(s), 1574(s), 1553(s), 1419(m), 1392(s), 1223(m), 1203(s), 1135(s), 1088(m), 1053(m), 855(m), 814(s), 788(m), 759(s), 740(m), 632(m), 578(m), 559(s). Syntheses of [Mn(HL)(2,2'-bipy)(H2O)]n (7). A mixture of Mn(OAc)2·4H2O (0.2 mmol), H3L (0.1 mmol), 2,2'-bipy (0.1 mmol), H2O (4 ml) and EtOH (1 ml) was placed in Teflon-lined stainless steel autoclave and heated to 180 ºC for 3 days, and then cooled to room temperature at a rate of 10 ºC·h−1. Light yellow block crystals of 7 were obtained in 43% yield based on H3L. Anal. Calcd for MnC24H19N2O7P (533.33): C, 54.05; H, 3.59, N, 5.25. Found: C, 54.55; H, 4.00, N, 5.02%. IR (KBr, cm−1): 3423(s), 3063(w), 1617(s), 1595(s), 1554(s), 1474(m), 1439(m), 1389(s), 1161(s), 1136(s), 1082(s), 1018(s), 839(m), 801(m), 764(s), 738(m), 651(m), 556(m). X-ray Crystallography. Single-crystal X-ray diffraction data for compounds 1−7 were collected on a Bruker Smart APEX-II CCD diffractometer using graphitemonochromatized Mo Kα radiation (λ = 0.71073 Å) using the φ-ω scan technique at room temperature. Data reduction was conducted with the Bruker SAINT package. Absorption correction was performed using the SADABS program. The structure was solved by the direct methods and refined on F2 by full-matrix least-squares using SHELXL program47 with anisotropic displacement parameters for all non-hydrogen atoms. Some disordered atoms (C78 and O33 in 4) were split over two sites, with a total occupancy of 1. Hydrogen atoms were introduced in calculations using the riding model. The crystallographic data and selected bond lengths for 1−7 are listed in Table 1 and Table S1, respectively. Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center. CCDC 1481704-1481710 contain the details of 1−7. RESULTS AND DISCUSSION Synthesis. In this work, we capitalize H3L as primary ligand and two N-donor ligands as auxiliary ligand to garner good quality single crystals of compounds 1−7 under hydro(solvo)thermal conditions based on the

following design (Scheme 2). Previously, we have prepared two 2-D silver(I) coordination polymers with symmetric or noncentrosymmetric architecture based on H3L by adjusting the metal-ligand ratio.27 To further explore the H3L coordination characteristics, we introduced auxiliary ligands 4,4'-bipy and 2,2'-bipy into the carboxyphosphinate reaction system corresponding Zn(II), Cd(II) and Mn(II) salts. Thus, seven novel coordination polymers with diverse structures are harvested, which exhibit 1-D chain, 2-D network and 3-D framework. Obviously, the N-donor auxiliary ligands and the metal ions have a significant influence on the structure features of 1−7. Although the deprotonation processes of H3L are completed by hydro(solvo)thermal reactions in mixed solvents without any basic additive (except triethylamine was added in 1), the solution pH value may be varied by regulating of the N-heterocyclic auxiliary ligands.48,49 Among these compounds, the 2,2'-phosphinico-dibenzoic acid (H3L) are completely deprotonated except partly deprotonated carboxylic ligand (HL2−) in 3 and 7, which were confirmed by the single crystal structure analysis and IR spectra.

Scheme 2 Synthesis scheme of compounds 1−7. Structure of [Zn3L2(H2O)4]n·2nH2O (1). Compound 1 crystallizes in the triclinic Pī space group with one and a half Zn(II) centers, one L3− anion, two coordinated water molecules and one lattice water molecule in the asymmetric unit. As shown in Figure 1a, Zn1 locates at the inversion center of an octahedral sphere surrounded by four oxygens from two equivalent L3− ligands and two water molecules. Zn2 adopts a distorted square-pyramidal geometry, coordinated by three carboxyl oxygens, one phosphinic oxygen and one water molecule. The distorted τ parameter of geometry is 0.300, which clearly indicates that the coordinated geometry of Zn2 is very distortion toward trigonal-bipyramid.50 The phosphinic O3b occupies the apical position with a Zn2−O3b bond distance of 1.929(2) Å, which leads to Zn2 being out of the basal plane 0.700 Å. Four coordination bonds on basal plane are slightly longer, from 1.966(2) to 2.388(2) Å. H3L is fully deprotonated, and the L3− ligand connects four Zn(II) ions with its five oxygen atoms (Scheme 1a), resulting in a 1-D chain along the a-axis (Figure 1b). In the 1-D chain, Zn1 and Zn2 are linked to form a quadrangle ring by two O2 atoms and two O−P=O bridges. The quadrangle rings connect each other by sharing



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Zn1 to form a necklace inorganic chain (Figure 1c). Additional investigation of this architecture indicates that adjacent chains are connected into layer structure by hydrogen bond O7−H7A···O6 (-x+2, -y, -z+1) in the bc plane. Furthermore, the 2-D layers are connected to form a 3-D supramolecular framework by face-to-face π–π stacking interaction occurring between the neighboring layer aromatic rings, which come from the L3− ligands. The stacking distance between centroids of the benzene rings is 3.664 Å. The lattice water molecules are located in the spacing of the neighboring chains, which also enhance the stability of the 3-D supramolecular framework through hydrogen bonding interaction.

Figure 1. (a) Asymmetric unit of 1; (b) A 1-D infinite chain structure formed by Zn(II) and L3− with µ4-bridging mode along the a-axis; (c) 1-D inorganic chain. H atoms and lattice water omitted for clarity. Symmetry codes: a, -x+1, -y+1, -z+1; b, x+1, y, z. Structure of [Zn3L2(4,4'-bipy)2]n (2). When linear N-donor ligand 4,4'-bipy was added to react with H3L and Zn(OAc)2·2H2O, compound 2 with completely different structure of 1 was isolated. Compound 2 crystallizes in monoclinic C2/c space group and shows a 3-D framework. A view of the asymmetric unit with atoms labeling is illustrated in Figure 2a. The asymmetric unit is composed of one and a half Zn(II) ions, one fully deprotonated L3− anion, and two a half neutral auxiliary ligand 4,4'-bipy. Two Zn(II) centers are distinct. Zn1 occupies the inversion center of a trans-octahedral geometry, coordinated by four oxygen atoms (O2, O2a, O3 and O3a) and two nitrogen atoms (N1

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and N2b) from two equivalent L3− anions and 4,4'-bipy ligands. Zn2 adopts a distorted tetrahedral geometry, coordinated by two carboxyl oxygens, one phosphinic oxygen and one nitrogen from 4,4'-bipy. The distorted τ parameter of the tetrahedral geometry is 0.77 with a largest θ angle of 143.85(8)º, which is introduced by Houser to describe the geometry of a four-coordinate metal system.51 The L3− ligand shows similar coordination mode as that in 1, which connects four Zn(II) ions with its five oxygen atoms, leading to a similar 1-D [Zn3L2]n chain along the c-axis (Figure 2b). Due to the different coordinated geometry around Zn2, there is no inorganic chain observed in 2. When the coordinated water molecules in 1 were substituted by 4,4'-bipy in 2, the 1-D chains are connected into a layer structure by the 4,4'-bipy linker with N1 and N2 atoms (blue stick in Figure 2c) in the bc plane. Furthermore, the 2-D layers extend to a 3-D porous metal-organic framework strutted by another 4,4'-bipy linker with N3 and N3e atoms (green stick in Figure 2c).

Figure 2. (a) Asymmetric unit of 2; (b) A 1-D infinite chain structure; (d) 3-D MOF (blue stick: 4,4'-bipy with N1 and N2), green stick: 4,4'-bipy with N3 and N3e). H atoms omitted for clarity. Symmetry codes: a, -x, y, -z+1/2; b, x, y-1, z; c, -x, -y, -z+1; d, x, -y, z+1/2; e, -x+1/2, -y–1/2, -z–1. Structure of [Zn(HL)(2,2'-bipy)(H2O)]n (3) and [Mn(HL)(2,2'-bipy)(H2O)]n (7). Although the metal salts are different to prepare compounds 3 and 7, both compounds are iso-structural. Only the structure of 3 is discussed in detailed. Compound 3 crystallizes in monoclinic space group P21/c, which shows 1-D zigzag chain structure and consists of chelating 2,2'-bipy auxiliary ligand. As shown in Figure 3a, the asymmetric unit contains one Zn(II) ion, one partially deprotonated HL2− anion, one


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2,2'-bipy ligand as well as one coordinated water molecule. Zn1 adopts a cis-octahedral geometry completed by one chelating 2,2'-bipy ligand, two carboxyl oxygens (O1 and O2a), one phosphinic oxygen (O4) and one water oxygen (O7). HL2− anion exhibits a µ2-bridge mode with one O4 atom and coordinated carboxylate group (O1−C1−O2) (Scheme 1b). Another protonated carboxyl group (O6=C14−O5H) is uncoordinated. This is confirmed by different C−O bond lengths, C14=O6 is 1.209(3) Å and C14−O5 is 1.322(3) Å. The Zn(II) centers are linked by the O1−C1−O2 carboxylate group to form a 1-D zigzag chain along the b-axis (Figure 3b). In the solid state, the 1-D chains are joined together to form a supramolecular structure by π–π stacking interaction occurring between the aromatic rings and pyridyl rings.

compounds.52

Figure 3. (a) Asymmetric unit of 3; (b) 1-D zigzag chain. Symmetry codes: a, x+1, y+1/2, -z+1/2. Structure of {[Cd9L6(H2O)8]·4H2O}n (4). Compound 4 crystallizes in the triclinic Pī space group and exhibits a 3-D metal-organic framework. The asymmetric unit consists of nine distinct Cd(II) ions, six fully deprotonated L3− anions, eight coordinated water molecules together with four lattice water molecules (Figure 4a). It is notable that the nine Cd(II) ions display different distorted octahedron, pentagonal-bipyramid, capped trigonal-prism, and capped octahedron geometries, which is the first case that four different geometries were observed in one cadmium compound. Cd1 and Cd6 are seven-coordinated, showing [CdO7] capped trigonal-prism geometry formed by seven oxygen atoms from four L3− ligands, in which O11 or O29 locates on the capped site (Figure 4b). Cd2 presents a distorted pentagonal-bipyramidal geometry completed by six oxygen atoms from four L3− ligands and water O37 atom. Cd7 exhibits a capped octahedral geometry, in which the capped site is occupied by O31. Different from the aforementioned four seven-coordinated Cd(II) ions, the remaining five Cd(II) ions are six-coordinated and show distorted [CdO6] octahedral geometries. Cd3, Cd4 and Cd8 are circled by three L3− ligands and water molecules (O38, O39 and O42). Cd5 is surrounded by four L3− ligands and water O40 atom. Cd9 is coordinated by one L3− ligand and three water molecules (O43, O44 and O44e). All Cd−O bond lengths fall in the range of 2.012(10)−2.564(4) Å, which are normal as other reported Cd(II)-carboxylate



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Figure 4. (a) Asymmetric unit of 4; (b) polyhedra of Cd1-Cd4 (blue), Cd5-Cd8 (green) and Cd9 (yellow); (c) 2-D layer in the bc plane; (d) 3-D framework. H and C atoms omitted for clarity. Symmetry codes: a, -x+2, -y+1, -z; b, -x+1, -y+2, -z+1; c, x, y+1, z; d, -x+1, -y+1, -z+1; e, -x, -y+1, -z+1. There are six fully deprotonated L3− anions in compound 4. They adopt complicated µ4-, µ5- and µ6-bridging coordination modes, such as (η2:η1-µ2)-(η1:η2-µ2)-(η2:η1-µ2)-µ5, (η2:η1-µ3)-(η1:η2-µ2)(η2:η1-µ2)-µ6, (η1:η1-µ3)-(η1:η0)-(η0:η0)-µ4, and (η1: 1 1 1 1 0 η -µ3)-(η : η -µ2)-(η : η )-µ5 modes (Scheme 1c, 1d, 1e and 1f), to connect five, six and four cadmium ions, respectively. The coexistence of four coordination modes originating from six distinct L3− ligands in one compound is rarely observed in reported carboxyphosphinate compounds.53 To described the sophisticated structure of 4, the nine Cd(II) ions can be divided into three groups according to their situation in the architecture. The first group possesses Cd1, Cd2, Cd3 and Cd4, which are linked through four carboxylate and two phosphinate oxygen atoms to constitute a quadrilateral tetranuclear Cd4 subunit. Two symmetry-related Cd4 subunits are held together by two µ3-O atoms of carboxylate groups to form a centrosymmetric octanuclear Cd8 cluster (blue, Figure 4b), which is different from those reported in document.54 The second group includes Cd5, Cd6, Cd7 and Cd8, which are connected by four carboxylate and one phosphinate oxygen atoms to afford a linear Cd4 subunit. Moreover, two symmetry-related linear Cd4 subunits are jointed together by four carboxylate and two phosphinate oxygen atoms to generate a centrosymmetric octanuclear Cd8 cluster (green, Figure 4b), which is similar to the first group of Cd8 cluster. The third group only contains Cd9. Worth mentioning here, two symmetry-related Cd9 centers are bridged by two water molecules (O44 and O44e) to inverse into a dimer (yellow, Figure 4b). The octanuclear Cd(II) cluster of Cd1-Cd4 connects its four neighboring octanuclear Cd(II) cluster of Cd5-Cd8 by O−P−O groups in mutually perpendicular shape, resulting in a 2-D inorganic network on bc plane (Figure 4c). Furthermore, the 2-D networks are interconnected by the

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dimer of Cd9, generating a 3-D metal-organic framework, as depicted in Figure 4d. Structure of [Cd8L4(OH)2(OAc)2(4,4'-bipy)]n (5). Compound 5 crystallizes in the triclinic Pī space group and has a 2-D network structure. The asymmetric unit is constituted by four crystallographically independent Cd(II) ions, two L3− anions, one hydroxyl group, one acetate and half a 4,4'-bipy ligand (Figure 5a). Cd1, Cd2, and Cd3 are six-coordinated, displaying similar distorted octahedral geometry but different coordination environments. Cd1 is coordinated by three L3− anions, one 4,4′-bipy and one µ3-OH. Cd2 is surrounded by six oxygen atoms from three L3− anions. Cd3 is encircled by six oxygen atoms from three L3− anions and one µ3-OH. Cd4 is different with above three Cd(II) ions, which is five-coordinated by two L3− anions, one µ3-OH, and one acetate, generating a distorted [CdO5] trigonal-bipyramid geometry. Four distinct Cd(II) ions are linked via two carboxylate oxygens and two phosphinate oxygens to constitute a Cd4 subunit. It is interesting that such two symmetry-related Cd4 subunits are held together by two carboxylate µ2-O7 atoms to result in a ring-like Cd8 cluster (Figure 5b), which is different from those in compound 4. Two types of L3− ligands display different coordination modes as (η2:η1-µ2)-(η1:η1-µ4)- (η1:η1-µ2)-µ6 and (η1: η1-µ3)-(η1: η1-µ2)-(η2:η1-µ2)-µ5 bridges, and respectively connect with six or five Cd(II) centers (Scheme 1g and 1h). The octanuclear units are bridged by double phosphinate groups to form a 1-D chain along the a-axis (Figure 5c). Moreover, the chains are linked with bidentate 4,4'-bipy ligands to construct a 2-D network (Figure 5d).


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Crystal Growth & Design 4,4'-bipy linkers in the bc plane (Figure 6d).

Figure 5. (a) Asymmetric unit of 5; (b) ring-like octanuclear cluster containing two Cd1-Cd4 subunits; (c) 1-D chain along the a-axis; (g) 2-D network (blue stick represent 4,4'-bipy). H and C atoms omitted for clarity. Symmetry codes: a, -x+1, -y, -z+1. Structure of [Mn3L2(4,4'-bipy)(EtOH)(H2O)2]n (6). Compared to 2, reducing the stoichiometric ratio of metal salt and linear auxiliary ligand 4,4'-bipy, leads to a 2-D layered network of 6 isolated. Compound 6 crystallizes in the triclinic Pī space group. The asymmetric unit of 6 with atoms labeling is presented in Figure 6a, which is composed of one and a half Mn(II) ions, one fully deprotonated L3− anion, one half 4,4'-bipy ligand, one coordinated ethanol and two coordinated water molecules. Mn1 locates at the inversion center of an octahedral geometry, which composed of six oxygen atoms from two equivalent L3− anions and ethanol molecules. Mn2 adopts an elongated octahedral geometry, coordinated by two carboxyl oxygens, one phosphinic oxygen, one nitrogen from 4,4'-bipy and two water molecules. Mn2−N1 2.341(6) and Mn2−O5a 2.395(6) Å are longer than other bond lengths. The L3− ligand exhibits µ3-bridge mode, which connects three Mn(II) ions with its four oxygen atoms (Scheme 1i), resulting in a different 1-D zigzag chain to 3 along the b-axis (Figure 6b). In the 1-D chain, two Mn2 are linked by two O5 atoms to form a binuclear unit. Then, the dimer is bridged by Mn1 ion through O−P−O bridge (Figure 6c). Further, the adjacent chains are connected into a 2-D layered network by

Figure 1. (a) Asymmetric unit of 6; (b) 1-D infinite chain along the a-axis; (c) 1-D inorganic chain; (d) 2-D network. H atoms omitted for clarity. Symmetry codes: a, -x+2, -y, -z+1; b, -x+1, -y+1, -z. Comparison of Coordination Modes and Structural Diversity. H3L is fully deprotonated in 1, 2, 4, 5 and 6, and partly deprotonated as HL2– in 3 and 7. Each 2,2'-phosphinico-dibenzoate ligand connects two (3, 7), three (6), four (1, 2, 4), five (4, 5), or six (4, 5) metal ions in their 1-D (1, 3, 7), 2-D (5, 6), and 3-D (2, 4) polymeric structures. As presented in Scheme 1, 2,2'-phosphinico-dibenzoate ligand adopts a total of nine types of coordination modes, and act as bi-, tri-, tetra-, penta-, and hexa-dentate ligands in 1−7. In the coordination mode c, d, f, g and h, all the oxygen atoms coordinated to the metal ions, which are apt to form cluster due to the closer of carboxylic groups and phosphinic unit. The other coordination modes have one or more non-coordination oxygen atoms. In addition, varied coordination geometries around metal centers are observed in 1−7. The Zn(II) ions in 1 (Zn1), 2 (Zn1), and 3 adopt octahedral geometry, except a square-pyramidal Zn2 in 1 and a tetrahedral Zn2 in 2. Compound 4 possesses four seven- and five six-coordinated Cd(II) ions, while 5 has one trigonal-bipyramidal and three octahedral Cd(II) ions. All of Mn(II) ions in 6 and 7 show octahedral geometries. Although 2, 5 and 6 are prepared under the similar reaction condition, compound 2 is a 3-D MOF, whereas 5 and 6 show 2-D networks. Obviously, the coordination geometries, coordination modes of ligand and metal-ligand ratio influence the final structures of 1−7.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

PXRD and Thermogravimetric Analyses. In order to check the purities, powder X-ray diffraction (PXRD) analyses of the seven compounds were carried out at room temperature. As shown in Figure S1 (supporting information), the main peak positions of the experimental patterns of 1−7 are almost consistent with their simulated ones, demonstrating the single-phase purities of the products. To examine the thermal stabilities of compounds 1−7, thermogravimetric (TG) analyses were carried out (Figure S2, supporting information). The TG study of 1 shows an initial weight loss of 11.0% (11.9% calcd) in 90-170 °C range, suggesting the loss of two lattice water and four coordinated water molecules. The anhydrous compound is thermally stable to 380 °C, and then successively decomposes. Anhydrous compound 2 is stable to 175 °C. The first weight-loss step in 175-235 °C is responding to release a 4,4'-bipy ligand (found 14.5%, calcd 14.0%). After 300 °C, the intermediate successively decomposes. Compounds 3 and 7 are two iso-structural compounds. Compound 3 releases solvent water and a coordinated water molecule in 50 -130 °C. After 200 °C, the anhydrous compound successively decomposes. Compound 7 releases a coordinated water molecule in 70 -130 °C (found 3.5%, calcd 3.4%). After 160 °C, the anhydrous compound successively decomposes. Compound 4 releases four lattice water molecules and eight coordinated water molecules in 35 -145 °C (found 7.9%, calcd 7.1%). After 285 °C, the anhydrous compound successively decomposes. Anhydrous compound 5 is thermally stable until 335 °C, and then rapidly decomposes. Compound 6 releases two coordinated water molecules in 65 -150 °C (found 2.5%, calcd 3.3%). The coordinated EtOH molecule may have released before the thermal analysis. The anhydrous compound is stable to 210 °C, and then successively decomposes. Photoluminescent Properties. The solid-state emission spectra of Zn(II)/Cd(II) compounds 1–5 were measured at room temperature (Figure S3). The main emission peak of free H3L is at 356 nm with excitation at 317 nm, which should be attributed to the π* → n or π* → π transitions.55,56 Meanwhile, the emission peak of bipyridine ligand is about 428 nm (λex = 350 nm) according to the literature.57 Compounds 1–3 show emission peaks at 375, 383 and 360 nm (λex = 317 nm), which are red-shifted by 19, 27 and 4 nm relative to the H3L ligand, respectively. For 4, the emission peak appears at 355 nm (λex = 317 nm) and is overlapped with that of free H3L ligand. However, compound 5 exhibits an emission peak at 346 nm (λex = 317 nm), which is blue shifted by 10 nm with respect to the free H3L ligand. Since the d10 Zn(II)/Cd(II) compounds are difficult to oxidize or reduce, their emissions through metal-to-ligand or ligand-to-metal charge transfer are less probable.58 The slightly emission energies shift of

Page 8 of 12

compounds 1–5 to H3L ligand indicate that their luminescent mechanism can be attributed to ligand-centered emission.59 Magnetic Properties. The temperature dependent magnetic susceptibility of 6 and 7 were measured under a 1000 Oe DC magnetic field for T = 2–300 K. Magnetic data as plots of χMT and χM−1 versus T are depicted in Figure 7. At room temperature, the χMT value of 6 is 13.72 emu K mol–1, which is slightly higher than the spin-only value (13.14 emu K mol–1) of three isolated MnII (S = 5/2) ions assuming g = 2.0. Upon cooling, χMT smoothly decreases and reaches 3.82 emu K mol–1 at 2 K, indicating antiferromagnetic interactions occurred. The magnetic susceptibility data follows the Curie–Weiss law with C = 14.07 emu K mol–1 and θ = –6.0 K. The C value corresponds to the value expected for Mn(II) ion with g = 2.06. The negative θ suggests antiferromagnetic interaction between Mn(II) ions. In 6, there is a 1-D chain constructed from binuclear Mn2−O5−Mn2a units and Mn1 ion by phosphinate groups. Compared to the oxygen bridge, the coupling interaction between the Mn(II) ions mediated by the O−P−O group might be negligible. To estimate the magnitude of the antiferromagnetic coupling, the isotropic spin Hamiltonian H = –2J (SMn2SMn2a) was used for the dimer with SMn = 5/2, where J is the coupling constant mediated by oxygen bridges. When the isolated Mn1 ion is taken into account, the expression was written by the Kambe method 60, 61 as follows: χM =

2 Ng 2 β 2 55e 30 J / kT + 30e 20 J / kT + 14e12 J / kT + 5e 6 J / kT + e 2 J / kT 35 Ng 2 β 2 × + 30 J / kT 20 J / kT 12 J / kT 6 J / kT 2 J / kT kT 11e + 9e + 7e + 5e + 3e +1 12kT

With this equation, the calculated results in the temperature range from 7 to 300 K are J = –1.01 cm–1, and g = 2.07 with R = Σ[(χMT)calc–(χMT)obs]2/Σ(χMT)obs2 = 2.9 × 10–3. These results confirm the existence of weak antiferromagnetic coupling within the binuclear Mn(II) unit mediated by oxygen bridges, which consists with the structural parameter (Mn2−O5−Mn2a = 105.03º). As shown in Figure 7, the linear fit of compound 7 via Curie–Weiss law reveals the C = 4.49 emu K mol–1 and θ = –1.5 K. The experimental χMT value (4.51 emu K mol–1) at room temperature is slightly higher than the calculated value of 4.38 emu K mol–1 for a noninteracting Mn(II) ion (S = 5/2, g = 2), which almost keeps a constant until 100 K. The rapid decreases of χMT below 40 K is indicative of antiferromagnetic coupling between the Mn(II) centers. According to the structure analysis, 7 is a 1-D uniform chain, in which Mn(II) centers are joined by carboxylate groups. Thus, the data is fitted by uniform chain model in the whole temperature range.62-65

Ng 2 β 2 1 + u S ( S + 1) 3kT 1 − u where u = coth(JS ( S + 1) / kT ) − kT / JS ( S + 1)

χ chain =

The best fit parameters are J = –0.10 cm−1 and g = 2.03,


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which indicates the presence of a very weak antiferromagnetic interaction between Mn(II) ions via the connection of carboxylate bridges.

ASSOCIATED CONTENT Supporting Information. X-ray crystallographic data in CIF format, selected bond lengths and bond angles, photoluminescent properties for 1-5, PXRD curves and TGA for 1−7 are available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author: *E-mail: zxwang@ shu.edu.cn (Z.-X.W.). Fax: +86-21-66132670 (Z.-X.W.). Notes: The authors declare no competing financial interest. ACKNOWLEDGMENTS This work was financially supported by Natural Science Foundation of Shanghai (16ZR1411400) and National Natural Science Foundation of China (21203117, 21271143 and 21171115).

(6)

REFERENCES

(7) Figure 7. Temperature dependence of the χMT and χM−1 product for 6 and 7. The solid lines are the best fits obtained from the models described in the text. CONCLUSIONS In summary, we have successfully synthesized and characterized seven new coordination polymers exhibiting various types of architectures constructed from a carboxylphosphinate ligand. The carboxylphosphinate exhibits varied coordination modes in them. Compound 1 is a 3-D supramolecular framework containing a 1-D necklace-like inorganic chain. Compound 2 is a 3-D porous MOF based on 1-D [Zn3L2]n chain held by two different 4,4'-bipy linkers. Compound 3 and 7 show 1-D zigzag chain structures. Compound 4 exhibits a sophisticated 3-D MOF constructed from two types of Cd8 cluster and one Cd2 dimer as building blocks, which is the first example showing the coexistence of four L3− coordination modes and four Cd(II) coordination geometries in one network. Compound 5 displays a 2-D network building with ring-like Cd8 clusters. Compound 6 shows a 2-D layered network with 4,4'-bipyridine linker. The similar emission energies of compounds 1−5 5 are attributed to ligand-centered emission. Variable-temperature magnetic analyses reveal weak antiferromagnetic couplings between the Mn(II) ions in compounds 6 and 7.

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Table 1. Crystallographic Data and Structure Refinement for Compounds 1-7 Compound

2

3

4

Zn3C28H28O18P2

Zn3C48H32N4O12

ZnC24H19N2O7P

Cd 9 C 84 H72 O48 P 6

Cd4C35H24NO15P2

Mn3C42H44N2O18P2

MnPC24H19N2O7

Formula weight

910.55

P2 1114.96

543.75

3046.84

1210.09

1091.56

533.33

Crystal system

Triclinic

Monoclinic

Monoclinic

Triclinic

Triclinic

Triclinic

Monoclinic

Space group

Pī

C2/c

P21/c

Pī

Pī

Pī

P21/c

a(Å)

7.3314(9)

29.4749(17)

13.8066(11)

14.936(2)

11.6564(19)

8.62(3)

13.891(3)

b(Å)

10.5605(13)

11.4469(8)

7.9228(6)

16.743(3)

12.215(2)

11.08(3)

7.9234(14)

c(Å)

10.8362(13)

14.6821(9)

21.0908(18)

20.093(3)

14.430(2)

11.77(4)

21.274(4)

α(deg)

82.1230(10)

90

90

86.491(2)

68.595(2)

88.95(4)

90

β(deg)

80.6650(10)

118.8980(10)

105.5190(10)

81.783(2)

70.538(2)

86.25(4)

104.954(4)

γ(deg)

76.2120(10)

90

90

84.549(2)

78.361(2)

82.03(4)

90

V (Å3)

799.76(17)

4336.9(5)

2222.9(3)

4945.0(14)

1796.1(5)

1111(6)

2262.2(7)

Z

1

4

4

2

2

1

4

Dc (g cm−3)

1.891

1.707

1.625

2.046

2.238

1.632

1.566

µ (mm−1)

2.416

1.793

1.228

2.089

2.502

0.992

0.705

F (000)

460

2256

1112

2964

1166

559

1092

Rint

0.0201

0.0214

0.0155

0.0268

0.0248

0.0151

0.0295

GOF

1.070

1.157

1.085

1.012

1.055

1.042

1.060

R1a,wR2b [I>2σ(I)] (I)]

0.0356, 0.1033

0.0284, 0.0858

0.0240, 0.0790

0.0802, 0.2268

0.0634, 0.1795

0.0277, 0.0743

0.0339, 0.1010

R1, wR2 (all data)

0.0372, 0.1048

0.0343, 0.0956

0.0267, 0.0868

0.1013, 0.2494

0.0775, 0.1910

0.0314, 0.0763

0.0482, 0.1210

Formula

a

1

5

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


6

7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 12

For Table of Contents Use Only Structural Diversity and Magnetic Properties of Seven Coordination Polymers Based on 2,2'-Phosphinico-dibenzoate Ligand Zhao-Xi Wang, Lin-Fei Wu, Hong-Ping Xiao, Xing-Hua Luo, Ming-Xing Li Seven novel metal-carboxylphosphinate coordination polymers exhibit diversity from 1-D, 2-D to 3-D architectures. Compound 4 exhibits a sophisticated 3-D MOF constructed from two types of Cd8 clusters and one Cd2 dimer, in which the coexistence of four coordination modes for ligand and four coordination geometries of metal ion was observed. Magnetic analyses reveal weak antiferromagnetic couplings between the Mn(II) ions in compounds 6 and 7.


Structural Diversity and Magnetic Properties of Seven Coordination

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