Isopolymolybdate-Based Cobalt/Nickel Coordination Polymers Constructed by V‑Type N‑Donor Ligands

• Published in: Inorganic chemistry 2021-01, Vol.60 (2), p.1264-1273
• Main Authors: Shi, Ya-Jie, Chen, Lin-Lin, Liu, Ying, Wu, Ying-Ying, Li, Ya-Min, Dang, Dong-Bin, Bai, Yan
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c03433

Four novel isopolymolybdate-based coordination polymers (CPs), constructed from 2,6-bis­(1,2,4-triazol-1-yl)­pyridine (btp), 1,3-bis­(4H-1,2,4-triazol-4-yl)­benzene (btb), and 3,5-bis­(1-imidazolium)­pyridine (bip), have been synthesized under a hydrothermal method: {[Co­(btp)­(H2O)2(β-Mo8O26)0.5]·3H2O} n (1), [Ni­(btp)­(H4Mo6O22)0.5] n (2), [Co­(btb)­(H2O)­(β-Mo8O26)0.5] n (3), and {[Co­(Hbip)2(H2O)2(γ-Mo8O26)]·6H2O} n (4). Complex 1 exhibits one 3D framework with an unexpected 3-nodal 2,4,6-c net topology containing the 1D {β-Mo8O26} n chains, 6-connected CoII centers, and V-type coordinated btp ligands. The neighboring [Mo6O22]4– anions of complex 2 are bridged by the NiII centers to build one 2D {Ni2(Mo6O22)} network, which is arranged into the 3D framework through the weak π···π stacking interactions. In compound 3, one 3D framework is formed by the adjacent 1D {Co2(btp)2} n chains connected by {β-Mo8O26} n units, which demonstrates a rare 4,6-c fsc topology. In complex 4, one 2D {Co­(Hbip)2(γ-Mo8O26)} layer with a (4, 4) network is connected to one 3D hydrogen-bonding framework via N-H···O and O-H···O hydrogen bonds. Magnetic data indicate that complexes 1 and 4 exhibit antiferromagnetic behaviors, whereas complexes 2 and 3 reveal spin-canting magnetic behavior and metamagnetic behavior, respectively. In addition, the proton conductivity of complexes 3 and 4 was investigated, showing that compound 4 has good proton conductivity at 85 °C and a relative humidity of 98% RH.