The self-assembly of a macrocyclic tetradentate ligand, cobalt(II) tetrafluoroborate, and nonlinear pseudohalides (dicyanamide and tricyanomethanide) has led to two cobalt(II) complexes, {[Co(L)(μ1,5-dca)](BF4)·MeOH}n (1) and [Co2(L)2(μ1,5-tcm)2](BF4)2 (2) (L = N,N'-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane; dca- = dicyanamido; tcm- = tricyanomethanido). Both complexes were characterized by single-crystal X-ray diffraction, spectroscopic, magnetic, and electrochemical studies. Structural analyses revealed that 1 displays a one-dimensional (1D) coordination polymer containing [Co(L)]2+ repeating units bridged by μ1,5-dicyanamido groups in cis positions, while 2 represents a discreate dinuclear cobalt(II) molecule bridged by two μ1,5-tricyanomethanido groups in a cis conformation. Both complexes have a CoN6 coordination environment around each cobalt center offered by the tetradentate ligand and cis coordinating bridging ligands. Complex 1 exhibits a high-spin (S = 3/2) state of cobalt(II) in the temperature range of 2-300 K with a weak ferromagnetic coupling between two dicyanamido-bridged cobalt(II) centers. Interestingly, complex 2 exhibits reversible spin-state switching associated with spin-spin coupling. Complexes 1 and 2 also exhibit interesting redox-stimuli-based reversible paramagnetic high-spin cobalt(II) to diamagnetic low-spin cobalt(III) conversion, offering an additional way to switch magnetic properties. A detailed theoretical calculation was consistent with the stated results.

Department of Inorganic Chemistry Faculty of Science Palacký University 17 listopadu 12 CZ 771 46 Olomouc Czech Republic

Solid State and Structural Chemistry Unit Indian Institute of Science Sir C 5 Raman Road Bangalore 560012 India

Univ Bordeaux CNRS Centre de Recherche Paul Pascal CRPP UMR 5031 33600 Pessac France

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Trigonally Distorted Hexacoordinate Co(II) Single-Ion Magnets