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

• Published in: Crystal growth & design 2024-09, Vol.24 (18), p.7466-7476
• Main Authors: Costa, Ines F. M., Franco, Chris H. J., Nesterov, Dmytro S., André, Vânia, Pereira, Laura C. J., Kirillov, Alexander M.
• Format: Article
• Language: English
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.4c00557

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.