Alkoxy-Bridged Dicopper(II) Cores Meet Tetracyanonickelate Linkers: Structural, Magnetic, and Theoretical Investigation of Cu/Ni Coordination Polymers.

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu(Hbdea)Ni(CN)] () and [Cu(dmea)Ni(CN)]·HO (), were successfully self-assembled in water by reacting Cu(II) nitrate with Hbdea (-butyldiethanolamine) and Hdmea (,-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)]. These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu(μ-aminopolyalcoholate)] is bridged by diamagnetic [Ni(CN)] linkers, resulting in 1D () or 2D () metal-organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling ( = -602.1 cm for and -151 cm for ) between Cu(II) ions within the dimers mediated by the μ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.