The Ground Spin States of Tris[p-(N-oxyl-N-tert-butylamino)phenyl] amine, -Methyl, and -Borane. Prospects of Further Studies

• Published in: Journal of solid state chemistry 2001-07, Vol.159 (2), p.428-439
• Main Authors: Itoh, Tetsuji, Matsuda, Kenji, Iwamura, Hiizu, Hori, Kenzi
• Format: Article
• Language: English
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1006/jssc.2001.9171

An exploratory study has been carried out on new poly(aminoxyl) radicals as potential bridging ligands for 2p/3d-hybrid-spin metal complexes having network structures. Temperature dependence of the magnetic susceptibility data on the title amine N in the range 2–300 K was analyzed to show that its ground state was a doublet with a quartet state lying 559 K (=1.11 kcal mol−1) above the doublet. B3LYP/6-31G*//B3LYP/6-31G computations on a simplified model molecule (N′) confirmed the doublet ground state by 0.84 kcal mol−1. The methyl compound (C) is a triplet diradical with a singlet state lying 410 K above the triplet. The hexamethyl derivative (B′) of the title borane B has a doublet ground state with an energy gap to a quartet state by 9.9 K. The electronic structures are described qualitatively by p-(N-oxyl-tert-butylamino)phenyl homologues of (·H2C)3X in which X=N,C·, and B atoms, and carries two, one, and no π-electrons, respectively. N and B′ showed two reversible redox waves. MnII(hfac)2 and C gave a black–violet crystalline complex in which the 3d and 2p spins ordered at 60 K.