Homoleptic, four-coordinate azadipyrromethene complexes of d10 zinc and mercury.
Tetraarylazadipyrromethenes, and especially their boron chelates, are a growing class of chromophores that are photoactive toward red light. The coordination chemistry of these ligands remains to be explored. Reported here are four-coordinate zinc(II) and mercury(II) complexes of tetraarylazadipyrromethene ligands. The new complexes contain two azadipyrromethenes bound per d(10) metal center and are characterized by (1)H NMR, optical absorption spectroscopy, X-ray diffraction crystallography, and elemental analysis. Solid-state structures show that these bis-chelate complexes distort significantly from idealized D2d symmetry. AM1 geometry optimizations indicate relaxation energies in the range of 6.8-15.2 kcal mol(-1); interligand pi-stacking provides an added energetic impetus for distortion. The absorption spectra show a marked increase in the absorption intensity in the red region and, in the case of the zinc(II) complexes, the development of a second distinct absorption band in this region, which is red-shifted by ca. 40-50 nm relative to the free ligand. Semiempirical INDO/S computations indicate that these low-energy optical absorptions derive from allowed excitations among ligand-based orbitals that derive from the highest occupied molecular orbital and lowest unoccupied molecular orbital of the free azadipyrromethene.
Teets
Thomas S
TS
Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106, USA.
Partyka
David V
DV
Updegraff
James B
JB
Gray
Thomas G
TG