Hetero-metallic frameworks of [Pd(CN)4]2− and Cu(II) with triamines: A rare example of a tetracyanometallate bridged 2D coordination polymer

Four cyano bridged Cu(II)–Pd(II) heterometallic complexes, [Cu(dpt)Pd(CN)4]n (1), {[Cu2(medpt)2Pd(CN)4](ClO4)2 · 3H2O}n (2), {[Cu2(dien)2Pd(CN)4](ClO4)2 · 2CH3OH}n (3) and {[Cu2(iPrdien)2Pd(CN)4](ClO4)2 · 2H2O}n (4) [dpt = 3,3′-iminobispropylamine; medpt = 3,3′-diamino-N-methyldipropylamine; dien = diethylenetriamine and iprdien = N′-isopropyldiethylenetriamine] have been synthesized and characterized by single crystal X-ray diffraction analysis, magnetic measurement and thermal study. Complexes 1, 2 and 3 are 1D coordination polymers, while 4 presents a 2D network. In 1, the cis-directed cyanide ligands of [Pd(CN)4]2− anions link two Cu(dpt) units to form a neutral coordination polymer, whereas in 2, 3 and 4, all the cyanide groups of [Pd(CN)4]2− take part in bonding with four adjacent Cu(II) ions, resulting in cationic coordination polymers counterbalanced by perchlorate anions. The structures are compared with those of analogous [Ni(CN)4]2− derivatives. The magnetic behavior shows antiferromagnetic interactions in all the complexes.

Graphical abstractCu(II)–Pd(II) heterometallic complexes, [Cu(dpt)Pd(CN)4]n (1), {[Cu2(medpt)2Pd(CN)4](ClO4)2 · 3H2O}n (2), {[Cu2(dien)2Pd(CN)4](ClO4)2 · 2CH3OH}n (3) and {[Cu2(iPrdien)2Pd(CN)4](ClO4)2 · 2H2O}n (4) [dpt = 3,3′-imino bispropylamine; medpt = 3,3′-diamino-N-methyldipropylamine; dien = diethylenetriamine and iprdien = N′-isopropyldiethylenetriamine] have been synthesized and characterized by single crystal X-ray diffraction analysis, magnetic measurement and thermal study. Complex 4 is a rare example of a tetracyanometallate bridged 2D coordination polymer.Figure optionsDownload full-size imageDownload as PowerPoint slide