Redox Ladder of Ni3 Complexes with Closed-Shell, Mono-, and Diradical Triphenylene Units: Molecular Models for Conductive 2D MOFs.

Abstract

We report the isolation and characterization of a series of trinickel complexes with 2,3,6,7,10,11-hexaoxytriphenylene (HOTP), [(Me3 TPANi)3 (HOTP)](BF4 )n (Me3 TPA=N,N,N-tris[(6-methyl-2-pyridyl)methyl]amine) (n=2, 3, 4 for complexes 1, 2, 3). These complexes comprise a redox ladder whereby the HOTP core displays increasingly quinoidal character as its formal oxidation state changes from -4, to -3, and -2 in 1, 2, and 3, respectively. No formal oxidation state changes occur on Ni, allowing the isolation of singlet diradical, monoradical, and closed-shell configurations for HOTP in 1, 2, and 3, respectively, with a concomitant decrease in the spin coupling strength upon oxidation. Because the three complexes can be considered models of the smallest building blocks of 2D conductive metal-organic frameworks such as Ni9 HOTP4 , these results serve as possible inspiration for the construction of extended materials with targeted electric and magnetic properties.