LUMINESCENT GOLD(I) COMPLEXES - OPTICAL AND ODMR STUDIES OF MONONUCLEAR HALO(TRIPHENYLPHOSPHINE)GOLD(1) AND HALO(TRIPHENYLARSINE)GOLD(I) COMPLEXES

Crystals of Ph(3)PAuX and Ph(3)AsAuX where Ph = phenyl and X = Cl and Br exhibit dual phosphorescences from two excited states. The higher energy system achieves a maximum relative intensity at low temperatures. Its origin is at approximate to 360 nm in all of the complexes, and it is assigned to an intraligand phosphorescence from a phenyl localized (3) pi pi* state. The zero-field-splitting parameters of the state are \D\ approximate to 0.2 and \E\ approximate to 0.04 cm(-1). The lower energy system has its origin at approximate to 460 nm in all of the complexes and tentative splitting parameters of \D\ approximate to 0.09 and \E\ approximate to 0.005 cm(-1). The phosphorescence rates of the individual spin levels at 1.4 K range from approximate to 5 x 10(3) to approximate to 10 s(-1), with the higher energy system having the larger rates. SCF-X alpha-SW calculations on H3PAuCl, H(2)PhPAuCl, Ph(3)PAuCl, PhPH(3)(+), and PhH are also reported for comparison with the experimental results.