Intraligand charge transfer in the Pd(II) oxinate complex Pd(qol)2. Site-selective emission, excitation, and optically detected magnetic resonance

The first spectroscopic investigation of Pd(qol)2 (qol- = 8-quinolinolato-N,O = oxinate) dissolved in an n-octane matrix (Shpol'skii matrix) is reported. Application of several spectroscopic methods at liquid helium temperatures (typically, T = 1.2 K), such as site-selective and highly resolved luminescence and excitation spectroscopy, time-resolved emission spectroscopy, optically detected magnetic resonance, microwave recovery, phosphorescence microwave double-resonance, and magnetic fields, allows us to characterize the lowest excited electronic states in detail. In accord with previous assignments for the related Pt(qol)2 it is shown that these lowest states represent-intraligand charge-transfer states, namely, 1ILCT and 3ILCT. The electronic origin of the 1ILCT state lies at 20,617 cm(-1) (site A). It exhibits a nearly homogeneous line width with a half-width of about 80 cm(-1) (fwhm), which corresponds to a lifetime of tau(1ILCT) approximately equals 2 x 10(-13) s. This value is even shorter than that found for Pt(qol)2, presumably due to intersystem crossings and relaxations to dd* states. The electronic origin of the 3ILCT state lies at 16 090 cm(-1) (site A), and its zero-field splittings (zfs) into three sublevels are 2E = 2356 MHz (0.0785 cm(-1)) and D - E = 5241 MHz (0.175 cm(-1)). The emission decay times of the three sublevels are determined as tauI = 90 +/- 30 ms, tau(II) = 180 +/- 10 mus, and tau(II) = 80 +/- 10 mus. (Slightly different values are found for a second site B at 16,167 cm(-1).) From the small values of zfs and the long emission decay times it is concluded that metal-d or MLCT admixtures to 3ILCT are very small. This result clearly reflects the ligand-centered character of the transition. The assignment as an ILCT transition is supported by the occurrence of relatively strong vibrational satellites of Pd-N and Pd-O character in highly resolved emission spectra. Although the transition is ascribed to a charge-transfer process, the geometry changes between the ground state and 3ILCT are very small. The results found for Pd(qol)2 are compared to those of companion studies of Pt(qol)2 and Pt(qtl)2 (qtl- = 8-quinolinethiolato-N,S).