Three transition metal organopolymolybdate hybrid compounds, namely, H2[Mn(H2O)4L3(γ-Mo8O26)] 8H2O (1), H[M2(CH3O)(H2O)6L3(γ-Mo8O26)] [M = Zn (2) and Co (3)] [L = 1,4-bis(3-pyridinecarboxamido)benzene] have been synthesized under solvothermal conditions and characterized by IR spectroscopy, TG analysis, powder XRD and single-crystal X-ray diffraction. Compounds 1–3 were obtained by the one-pot method, and the mixture of methanol and water with different ratios was used as the solvent. In compound 1, the γ-Mo8 anions were connected with pyridine groups of ligand L by the Mo–N bond, forming an uncommon 1D γ-Mo8–L chain. The adjacent chains were connected by [MnL2(H2O)4]2+ moieties through hydrogen bonding interaction to construct a 2D supramolecular network. Compounds 2 and 3 are isostructural, which show a 3D 2,4,6-connected {44·62}{44·66·84·10}{6} framework. The γ-Mo8 anions were connected by [M(H2O)2(CH3O)]+ [M = Zn (2) and Co (3)] subunits forming 1D M–Mo8 chains, which were connected by [ML2(H2O)4]2+ moieties to construct a 2D layer. In compounds 2 and 3, there also exist the same 1D γ-Mo8–L chains as in 1, which extended the 2D networks to 3D frameworks. The Mo–N bond with pyridyl groups was formed under the solvothermal conditions, which is scarcely reported to our knowledge. The effect of the solvent on the assembly of the title compounds and the formation of the Mo–N bond, as well as the role of metal–organic moieties on the construction of diverse organopolymolybdate compounds have been discussed in detail. Furthermore, the electrochemical and photocatalytic properties of 1–3 have been investigated.

•Five 2D bbbm-based transition-metal coordination polymers are obtained.•The racemization of D-(+)-camphoric acid and the reduction of CuII are observed in the preparation of five polymers.•The magnetic, thermostable and photoluminescent properties of five polymers are investigated.Five two-dimensional (2D) metal–organic coordination polymers, [M(D-cam)(bbbm)][M(L-cam)(bbbm)] [M = Co (1), Ni (2) and Zn (3)], [CuII(OH)(bbbm)(H2O)]2(NO3)2·2H2O (4) and [CuI(bbbm)2](HCOO) (5) [H2cam = camphoric acid and bbbm = 1,1-(1,4-butanediyl)bis-1H-benzimidazole], have been hydrothermally synthesized and structurally characterized. Complexes 1–3 are isostructural and possess three-dimensional (3D) supramolecular architectures based on two types of homochiral layers. Both 4 and 5 exhibit (4,4) layer structures, which are extended into 3D supramolecular architectures by hydrogen bonding and π–π stacking interactions, respectively. The magnetic properties of 4, as well as the thermostable and photoluminescent properties of 1–5 have been investigated.Five 2D bbbm-based transition-metal coordination polymers are synthesized. Racemization of D-(+)-camphoric acid and reduction of CuII are observed. Magnetic, thermostable and photoluminescent properties are investigated.

Three transition metal organopolymolybdate hybrid compounds, namely, H2[Mn(H2O)4L3(γ-Mo8O26)] 8H2O (1), H[M2(CH3O)(H2O)6L3(γ-Mo8O26)] [M = Zn (2) and Co (3)] [L = 1,4-bis(3-pyridinecarboxamido)benzene] have been synthesized under solvothermal conditions and characterized by IR spectroscopy, TG analysis, powder XRD and single-crystal X-ray diffraction. Compounds 1–3 were obtained by the one-pot method, and the mixture of methanol and water with different ratios was used as the solvent. In compound 1, the γ-Mo8 anions were connected with pyridine groups of ligand L by the Mo–N bond, forming an uncommon 1D γ-Mo8–L chain. The adjacent chains were connected by [MnL2(H2O)4]2+ moieties through hydrogen bonding interaction to construct a 2D supramolecular network. Compounds 2 and 3 are isostructural, which show a 3D 2,4,6-connected {44·62}{44·66·84·10}{6} framework. The γ-Mo8 anions were connected by [M(H2O)2(CH3O)]+ [M = Zn (2) and Co (3)] subunits forming 1D M–Mo8 chains, which were connected by [ML2(H2O)4]2+ moieties to construct a 2D layer. In compounds 2 and 3, there also exist the same 1D γ-Mo8–L chains as in 1, which extended the 2D networks to 3D frameworks. The Mo–N bond with pyridyl groups was formed under the solvothermal conditions, which is scarcely reported to our knowledge. The effect of the solvent on the assembly of the title compounds and the formation of the Mo–N bond, as well as the role of metal–organic moieties on the construction of diverse organopolymolybdate compounds have been discussed in detail. Furthermore, the electrochemical and photocatalytic properties of 1–3 have been investigated.