LAUSR

Abstract Two neutral coordination polymers of Cadmium(II) pseudohalide of the type [Cd(LL)($$\upmu _{1,5}$$μ1,5-$$\hbox {dca})_{2}]_{\mathrm{n}}$$dca)2]n (1) and [Cd(LL)($$\upmu _{1,3}$$μ1,3-$$\hbox {NCS})_{2}]_{\mathrm{n}}$$NCS)2]n (2) (LL = phenyl(pyridin-2-yl)methanimine and dca = dicyanamide) have been isolated using a 1:1:1:2 molar ratio of $$\hbox {CdCl}_{2}$$CdCl2.$$\hbox {H}_{2}\hbox {O}$$H2O, 2-aminopyridine (ap), 2-benzoylpyridine (bp) and Na(dca)/$$\hbox {NH}_{4}$$NH4SCN in alcoholic solvent at room temperature. X-ray structural study reveals that in the condensation reaction of ap and bp some degradation occurs in presence of the metal ion to afford an in situ generated bidentate Schiff base (LL) in the complexed form. Each Cadmium(II) center in both 1 and 2 adopts an octahedral geometry with a $$\hbox {CdN}_{6}$$CdN6 chromophore in 1 and a $$\hbox {CdN}_{4}\hbox {S}_{2}$$CdN4S2 chromophore in 2. In 1, each metal(II) center is connected to four other metal(II) centers through four different $$\upmu _{1,5}$$μ1,5-dca bridges affording a three-dimensional network structure, whereas each Cd(II) center in 2 is linked with neighbouring Cd(II) centers through bibridged end-to-end (EE) thiocyanates to form a non-ending linear 1D zig-zag chain. Further, in crystalline state 1D chains in 2 are stabilized through weak intermolecular C-H...S hydrogen bond interaction promoting 2D sheet structure. Thermally stable compounds 1 and 2 show intraligand $$^{1}(\uppi $$1(π-$$\uppi ^{*})$$π∗) fluorescence in DMF solution at room temperature.Graphical AbstractSynopsis: Two new coordination polymers of Cadmium(II) pseudohalide in combination with in situ generated bidentate Schiff base are isolated and X-ray crystallographically characterized. In 1, each Cd(II) center is connected with four different Cd(II) centers through four $$\upmu _{1,5}$$μ1,5-dca bridges affording a 3D network structure, whereas Cd(II) center in 2 is connected with neighbouring Cd(II) center through dibridged end-to-end thiocyanates to form a non-ending linear 1D zig-zag chain. 1D chains in 2 are stabilized through weak intermolecular C-H...S hydrogen bond interactions promoting 2D sheet structure. This work on such thermally stable compounds illustrates a potentially versatile approach towards isolation of uncharged luminous metal-organic frameworks.