Exploring the Assembly, Structures, and Magnetism of Cyanometallate-Driven Coordination Polymers

Two heterometallic cyanometallate-driven Cu(II)/Co(III) coordination polymers, [{Cu2K(H2tipa)2(H2O)4}Co(CN)6]n·4nH2O (1) and [{Cu2(H2tea)2}3{Co(CN)6}2]n·10nH2O (2), were self-assembled from Cu(NO3)2, an aminoalcohol chelator (H3tipa, triisopropanolamine; or H3tea, triethanolamine), and K3[Co(CN)6]. The compounds were fully characterized by single-crystal and powder X-ray diffraction, FTIR spectroscopy, and thermogravimetric and elemental analyses, revealing 1D (1) and 2D (2) metal–organic architectures with 2C1 and hcb topologies constructed from [Cu2K(H2tipa)2(H2O)2]3+ or [Cu2(H2tea)2]2+ blocks and [Co(CN)6]3– linkers. A detailed magnetic study of 1 and 2 was performed by variable-temperature magnetic susceptibility measurements and broken symmetry DFT calculations. These new compounds expand a family of heterometallic coordination polymers derived from hexacyanocobaltate(III) linkers, with compound 1 also representing the first structurally characterized heterotrimetallic Cu/Co/K derivative.