Seven coordination polymers, namely [Mn(4-cptpy)2]n (1), [Co(4-cptpy)2]n (2), [Mn3(4-cptpy)6(H2O)]n·2nH2O (3), [Co(4-cptpy)(HCOO)(H2O)]n·nDMF (4), [Zn2(4-Hcptpy)2Cl4]n·2nC2H5OH·nH2O (5), [Co4(3-cptpy)4(HCOO)4(H2O)2]n (6), and [Mn(3-cptpy)2]n (7) (4-Hcptpy = 4-(4-carboxyphenyl)-4,2':6',4''-terpyridine; 3-Hcptpy = 4-(4-carboxyphenyl)-3,2':6',3''-terpyridine), have been synthesized under hydro(solvo)thermal conditions and structurally characterized. A general solvothermal method is proposed for preparing carboxylate complexes in DMF solution without any basic additive. 1 and 2 possess isostructural 3D metal-organic frameworks containing nanosized cavities. 3 is a beautiful 2D coordination polymer assembled by flower-like Mn3(4-cptpy)6(H2O) subunits. 4 and 6 both display 2D polymeric networks constructed from 4/3-cptpy(-) ligands, in which the formate ligands originate from the hydrolysis of DMF. 5 is a 1D 2(1) helical chain polymer. 7 shows a 2D network with a (3.6) two-nodal kgd topology. 4/3-Hcptpy ligands display seven types of coordination modes. The zinc complex 5 emits strong violet luminescence. 1 and 2 are both thermally stable below 440 °C and exhibit antiferromagnetic interactions.

Six zinc metal–organic frameworks, namely, [Zn­(bpmb)­(HCOO)] n ·[Zn(bpmb)­(OH)] n ·​4nH2O (1), [Zn­(bpmb)­(HCOO)] n (2), [Zn2­(bpmb)2­(fum)] n ·​9nH2O (3), [Zn3­(bpmb)2­(d-cam)2] n (4), [Zn2­(bpmb)­(1,3,5-btc)] n ·​nDMA (5), and [Zn­(bpmb)­(1,2,4,5-H2btec)] n ·​4nH2O (6) (Hbpmb = 3,5-bis­(4-pyridyl­methoxy)­benzoic acid; H2fum = fumaric acid; d-H2cam = d-camphoric acid; 1,3,5-H3btc = 1,3,5-benzenetricarboxylic acid; 1,2,4,5-H4btec = 1,2,4,5-benzenetetracarboxylic acid; DMA = N,N-dimethylacetamide), were synthesized under solvothermal conditions. Their structures were characterized by EA, IR, PXRD, TG, and single-crystal XRD. Complex 1 is constructed of two independent neutral 3D MOFs with large 1D nanosized square channels, which are further entangled by each other to give an unexpected 4-fold [2 + 2] interpenetrating architecture. Complex 2 is a 3D MOF constructed from tetradentate bpmb and bidentate formate ligands, which is an isomer of the [Zn(bpmb)­(HCOO)] n piece in 1. Complex 3 displays a 2D double-layered network that possesses 1D nanosized pores. Each 2D double layer is further interlocked with two neighboring ones to form an interesting 3D polycatenation array. Complex 4 possesses a 2D network constructed from a trinuclear [Zn3­(COO)6­N4] cluster and Zn–cam double-helical chain. Complex 5 is a 3D porous MOF constructed from tridentate bpmb and hexadentate 1,3,5-btc ligands. Complex 6 exhibits a 2-fold interpenetrating 2D wavelike (4,4) network constructed from bidentate bpmb and 1,2,4,5-H2btec ligands. The bpmb ligand adopts four types of coordination modes in 1–6. The secondary carboxylate ligands have obvious effects on their coordination architectures. Tetrahedral-, octahedral-, and trigonal-bipyramidal geometries around Zn(II) ions are observed. A general solvothermal method is proposed for preparing carboxylate complexes in DMF−H2O solution without any basic additive. In the preparation of 3, maleic acid is converted to a fumarate ligand. The thermal stabilities of six complexes and N2 adsorption behaviors of 1 and 3 are investigated. All the Zn(II) complexes emit blue luminescence originating from ligand-centered emission.

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