The work in the present investigation reports the syntheses, structures, steady state, and time-resolved photophysical properties of a tetraiminodiphenol macrocyclic ligand H(2)L and its eight dinuclear zinc(II) complexes and one cadmium(II) complex having composition [Zn(2)L(H(2)O)(2)](ClO(4))(2)·2CH(3)CN (1), [Zn(2)L(H(2)O)(2)](ClO(4))(2)·2dmf (2), [Zn(2)L(H(2)O)(2)](NO(3))(2)·2dmf (3), [Zn(2)LCl(2)] (4), [Zn(2)L(N(3))(2)] (5), [Zn(2)L(NCS)(2)] (6), [Zn(2)L(NCO)(2)] (7), [Zn(2)L(NCSe)(2)](2)·dmf (8), and [Cd(2)L(OAc)(2)] (9) with various coordinating and noncoordinating anions. The structures of all the complexes 1-9 have been determined by single-crystal X-ray diffraction. The noncovalent interactions in the complexes result in the generation of the following topologies: two-dimensional network in 1, 2, 4, 6, 7, 8, and 9; three-dimensional network in 5. Spectrophotometric and spectrofluorometric titrations of the diprotonated salt [H(4)L](ClO(4))(2) with triethylamine as well as with zinc(II) acetate and cadmium(II) acetate have been carried out, revealing fluorescence enhancement of the macrocyclic system by the base and the metal ions. Steady state fluorescence properties of [H(4)L](ClO(4))(2) and 1-9 have been studied and their quantum yields have been determined. Time resolved fluorescence behavior of [H(4)L](ClO(4))(2) and the dizinc(II) and dicadmium(II) complexes 1-9 have also been studied, and their lifetimes and radiative and nonradiative rate constants have been determined. The induced fluorescence enhancement of the macrocycle by zinc(II) and cadmium(II) is in line with the greater rate of increase of the radiative rate constants in comparison to the smaller rate of increase of nonradiative rate constants for the metal complexes. The fluorescence decay profiles of all the systems, being investigated here, that is, [H(4)L](ClO(4))(2) and 1-9, follow triexponential patterns, revealing that at least three conformers/components are responsible to exhibit the fluorescence decay behavior. The systems and studies in this report have been compared with those in the reports of the previously published similar systems, revealing some interesting aspects.

The work in this investigation deals with the syntheses, characterization, crystal structures and catechol oxidase activity of four diphenoxo-bridged Co(III)Co(III) compounds of composition [Co(III)Co(III)L(Me-pn)(N3)4]·6H2O (), [Co(III)Co(III)L(Me-pn)(N3)4]·4H2O (), [Co(III)Co(III)L(Et-pn)(N3)4]·3.5H2O () and [Co(III)Co(III)L(Et-pn)(N3)4]·CH3CN·2.5H2O (), and two diphenoxo-bridged Co(III)Co(II) compounds of composition [Co(III)Co(II)L(Me-Me2pn)(N3)3]·2H2O () and [Co(III)Co(II)L(Et-Me2pn)(N3)3]·H2O (). In these compounds, H2L(Me-pn), H2L(Et-pn), H2L(Me-Me2pn) and H2L(Et-Me2pn) are four Robson type tetraiminodiphenolate macrocyclic ligands, in which the superscript Me and Et indicate that the dialdehyde components are 4-methyl-2,6-diformyl-phenol and 4-ethyl-2,6-diformyl-phenol, respectively, while pn and Me2pn indicate that the diamine components are 1,3-diaminopropane and 2,2-dimethyl-1,3-diaminopropane, respectively. The Co(III)Co(III) compounds are further characterized by (1)H NMR spectra. Compounds and are prepared following a metal-templated synthesis, while compounds and are prepared by direct synthesis, which includes using a pre-isolated macrocycle, [H4L(Me-pn)](ClO4)2/[H4L(Et-pn)](ClO4)2, as a reactant. On changing the diamine component of the corresponding macrocycle from 1,3-diaminopropane to 2,2-dimethyl-1,3-diaminopropane, but otherwise following the similar reaction procedure (both direct and template), the Co(III)Co(II) compounds [Co(III)Co(II)L(Me-Me2pn)(N3)3]·2H2O (), [Co(III)Co(II)L(Et-Me2pn)(N3)3]·H2O (), [Co(III)Co(II)L(Me-Me2pn)(N3)3]·0.5MeCN·0.27H2O (; Inorg. Chim. Acta, 2014, 412, 38) and [Co(III)Co(II)L(Et-Me2pn)(N3)3]·MeCN (; Dalton Trans., 2013, 42, 4561) are formed, rather than Co(III)Co(III) compounds. Like compounds and , all the compounds show catechol oxidase activity (substrate: 3,5-di-tert-butyl catechol). The kinetic parameters for , and have been determined. Their Kcat values are, respectively, 212.6, 188.0 and 191.3 h(-1). ESI-MS (positive) spectra of some representative cases (with and without the substrate) have been recorded and the positive species have been assigned well. Unprecedented and surprising aspects of the composition/structure and properties of the complexes in this investigation have been discussed.

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One phenoxo–hydroxo bridged tetranuclear cluster and one phenoxo-µ1,1-azido-µ1,3-azido bridged one-dimensional coordination polymer of copper(ii) derived from a Schiff base ligand are described.