Single-crystal electronic and electron spin resonance spectra of bis-(3-methylpentane-2,4-dionato)copper(II)

Abstract
The polarised single-crystal electronic and e.s.r.spectra of bis-(3-methylpentane-2,4-dionato)copper(II) are reported The e.s.r.spectrum indicates a dxy ground-state. The electronic spectra have been interpreted in D2h symmetry by use of a vibronic mechanism and an intensity borrowing mechanism yielding the tentative one-electron orbital sequence: dxy > dx2y2 > dxz > dz2, with the position of the dyz orbital uncertain but probably close to the dxz orbital. The combined spin–orbit and orbital reduction parameters are evaluated as r= 0·74 and r= 0·77 and suggest substantial π bonding, especially out-of-the-plane (contrary to previous suggestions). The high energy of the dz2dxy transition is consistent with the high tetragonal distortion present, with the short in-plane copper–oxygen bonds, and with the description of the complex as being strictly square-coplanar. Data for other bis-chelates of this type are also discussed.

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