A Synthetic, Structural, Spectroscopic and DFT study of Re-I, Cu-I, Ru-II and Ir-III Complexes Containing Functionalised Dipyrido[3,2-a:2 ',3 '-c]phenazine (dppz)

作者：Lundin Natasha J; Walsh Penny J; Howell Sarah L; Blackman Allan G; Gordon Keith C^*

来源：Chemistry - A European Journal, 2008, 14(36): 11573-11583.

DOI：10.1002/chem.200801369

• density functional calculations
• dipyridophenazine
• electronic structure
• ligand effects
• N heterocycles

The ligands 11-cyanodipyrido[3,2-a:2',3'-c]phenazine and 2-(11-dipyrido[3,2-a:2'3'-c] phenazine)-5-phenyl-1,3,4-oxadiazole have been coordinated to Re-I, Cu-I, Ru-II and Ir-III metal centres. Single-crystal X-ray analyses were performed on fac-chlorotricarbonyl(11- cyanodipyrido[3,2-a:2',3'-c]phenazine)rhenium (C22H9ClN5O3Re, a = 6.509(5) b = 12.403(5), c = 13.907(5) angstrom, alpha = 96.88(5), beta=92.41(5), gamma=92.13(5)degrees. triclinic, P (1) over bar, Z=2) and bis-2,2'-bipyridyl(2-(11-dipyrido[3,2-a:2'.3'-c]phenazine)-5- phenyl-1,3,4-oxadiazole)ruthenium triflate center dot 2 CH3CN (C52H36F6N12O8RuS2, a = 10.601(5), b = 12.420(5), c = 20-066(5) angstrom, alpha = 92.846(5) beta = 96.493(5), gamma = 103.720(5)degrees, triclinic, P (1) over bar, Z=2). The ground- and excited-state properties of the ligands and complexes have been investigated with a range of techniques, including electro-chemistry, absorption and emission spectroscopy, spectroelectrochemistry and excited-state lifetime Studies. Spectroscopic, time-resolved and DFT studies reveal that the ligand-centred (LC) transitions and their resultant excited states play an important role in the photophysical properties of the complexes. Evidence for the presence of lower-lying metal-to-ligand charge-transfer transitions is obtained from resonance Raman spectroscopy, but nanosecond transient Raman experiments suggest that once excited, the (LC)-L-3 state is populated.

• 出版日期2008