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Two novel 3d–4f coordination polymers [Ln(NiL)(Nipt)(C2O4)0.5 · H2O] · H2O (Ln = Er (I), Eu (II) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,13-dien; H2Nip = 5-nit-roisophthalic acid) were obtained by using 5-nitroisophthalate and mononuclear macrocyclic oxamide complex NiL as co-ligand to react with Ln(NO3)3 ⋅ 6H2O (Ln = Er, Eu) under solvothermal condition, and characterized by single crystal X-ray diffraction (CIF files CCDC nos. 1587618 (I) and 1587619 (II)). Two complexes are isostructural structure and exhibit a two-dimensional network architecture formed by [Ln(III)Ni(II)] units via the oxamide, 5-nitroisophthalate and oxalate bridges, and adjacent 2D structures are linked together with C–H⋅⋅⋅O and O–H⋅⋅⋅O intermolecular hydrogen bonds to form a 3D superamolecular architectures. The fluorescence properties of I and II are also characterized.

Three novel 3d–4f heterometal complexes [Ln(NiL)3(Btca)(NO3)] · xH2O (Ln = Sm(III) (I), Pr(III) (II), Eu(III) (III) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H2Btca = benzotriazole-5-carboxylic acid) were solvothermally synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1555557 (I), 1555555 (II), 1555556 (III)). They crystallized in the monoclinic space group P21/n for I (x = 1.5) and C2/c for (II) and (III) (x = 1), respectively. In these complexes, the central Ln(III) and external nickel ions are bridged by macrocyclic oxamide groups. The metal center of Ln(III) resides in a distorted bicapped square antiprism surrounding with six oxygen atoms of three oxamide groups, two oxygen atoms of Btca2– ion and two oxygen atoms of NO3-. Furthermore, there are C–H···O and/or C–H···N hydrogen bond interactions among nitrate, benzotriazole-5-carboxylate, macrocyclic oxamide and water to form three-dimensional superamolecular architecture. The fluorescence properties of the compounds I and II are also discussed.

A novel heterometallic coordination polymer {[Cd2(NiL)2(Btca)4] · H2O} n (I) (H2L = 2,3-dioxo5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H2Btca = benzotriazole-5-carboxylic acid) was synthesized and structurally characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction (CIF file CCDC no. 1043065). Complex I exhibits a two-dimensional network structure formed by Cd2Ni2 units via the oxamide and benzotriazole-5-carboxylate bridges. It crystallizes in the monoclinic system, space group P21/c. The lattice parameters are: a = 1.24488(8), b = 2.75370(19), c = 1.49336(10) A, β = 103.1070(10)° and V = 4.9859(6) A3, Z = 4. The fluorescence properties of compound I are also discussed.

Three complexes with the formula [Co(Ip)(CuL)(H2O)2] · H2O (I), [Co(Ip)(NiL)(H2O)2] · H2O (II), [Co(CuL)2(Hbtc)(H2O)] (III), (H2Ip = m-isophthalic acid; H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; H3Btc = 1,3,5-benzenetricarboxylic acid) were synthesized and structurally characterized by elemental analysis, IR and UV spectroscopy. Single-crystal X-ray analyses reveal that the complexes I and II contain neutral heterometallic binuclear CoM (for I and II, M = Cu, Ni, respectively) moieties, and complex III contains discrete neutral trinuclear CoCu2 moieties. The structures of I–III consist of two-dimensional supramolecular architecture formed by strong O-H…O intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I were investigated and discussed in detail.

One novel heterometallic trinuclear complex of macrocyclic oxamide [Ni(CuL)2(HBTC)H2O] (I) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,13-dien; H3BTC = 1,3,5-benzenetricarboxylic acid) has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, XRD, and single-crystal X-ray diffraction. The crystals crystallize in the monoclinic system, space group P21/c, a = 11.435(3), b = 20.646(5), c = 18.430(5) A, β = 94.131(4)°. The structure of I has oxamido-bridged trinuclear [Cu2IINiII] units and consists of two-dimensional supramolecular architecture formed by strong intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I was investigated and discussed in detail.

Macrocyclic and supermolecular complexes [Cu2(NiL)2Cl4] (I) and [Cd2(CuL)2Cl4] (II) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-diene) have been synthesized and structurally determined by X-ray diffraction and IR spectrum. Complex I crystallizes in the monoclinic system with P21/n group, a = 10.9019(15), b = 14.3589(19), c = 12.4748(17) 0A, β = 108.645(2)°, Z = 4. Complex II crystallizes in the monoclinic system with P21/n group, a = 10.9784(16), b = 14.580(2), c = 12.8904(18) A, β = 109.339(2)°, Z = 4.

The complex incorporating macrocyclic oxamide of the formula [(CuL)2Cd(NCS)2] (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-diene) has been synthesized and structurally characterized. The crystals crystallize in the monoclinic system, space group C2/c, a = 13.865(3), b = 14.390(3), c = 38.252(8) A, β = 92.45(3)°, Z = 8. The crystal structure unit is a trianuclear complex in which the Cd2+ and Cu2+ ions are bridged by the macrocyclic oxamide groups. The [(CuL)2Cd(NCS)2] units are alternately bridged by C-H···O to C-H···S hydrogen bond to form a 2D framework. The luminescent property of the compound is also discussed.