Study of the Counter Cation Effects on the Supramolecular Structure and Electronic Properties of a Dianionic...

Herein, we describe the synthesis, crystal structure, and electronic properties of {[K₂(dmso)(H₂O)₅][Ni₂(H₂mpba)₃]·dmso·2H₂O}_n (1) and [Ni(H₂O)₆][Ni₂(H₂mpba)₃]·3CH₃OH·4H₂O (2) [dmso = dimethyl sulfoxide; CH₃OH = methanol; and H₄mpba = 1,3-phenylenebis(oxamic acid)] bearing the [Ni₂(H₂mpba)₃]^2- helicate, hereafter referred to as {Ni^II₂}. SHAPE software calculations indicate that the coordination geometry of all the Ni^II atoms in 1 and 2 is a distorted octahedron (O_h) whereas the coordination environments for K1 and K2 atoms in 1 are Snub disphenoid J84 (D_2d) and distorted octahedron (O_h), respectively. The {Ni^II₂} helicate in 1 is connected by K⁺ counter cations yielding a 2D coordination network with sql topology. In contrast to 1, the electroneutrality of the triple-stranded [Ni₂(H₂mpba)₃] ^2- dinuclear motif in 2 is achieved by a [Ni(H₂O)₆]²⁺ complex cation, where the three neighboring {Ni^II₂} units interact in a supramolecular fashion through four R(10) homosynthons yielding a 2D array. Voltammetric measurements reveal that both compounds are redox active (with the Ni^II/Ni^I pair being mediated by OH^- ions) but with differences in formal potentials that reflect changes in the energy levels of molecular orbitals. The Ni^II ions from the helicate and the counter-ion (complex cation) in 2 can be reversibly reduced, resulting in the highest faradaic current intensities. The redox reactions in 1 also occur in an alkaline medium but at higher formal potentials. The connection of the helicate with the K⁺ counter cation has an impact on the energy levels of the molecular orbitals; this experimental behavior was further supported by X-ray absorption near-edge spectroscopy (XANES) experiments and computational calculations.