Blue phosphorescence from mixed cyano-isocyanide cyclometalated iridium(III) complexes.
The synthesis, structure, and photophysical and electrochemical properties of cyclometalated iridium complexes with ancillary cyano and isocyanide ligands are described. In the first synthetic step, cleavage of dichloro-bridged dimers [Ir(N=C)2(mu-Cl)]2 (N=C = 2-phenylpyridine, 2-(2-fluorophenyl)pyridine, and 2-(2,4-difluorophenyl)pyridine) by isocyanide ligands gave monomeric species of the types Ir(N=C)2(RNC)(Cl) (RNC = t-butyl isocyanide, 1,1,3,3-tetramethylbutyl isocyanide, 2-morpholinoethyl isocyanide, and 2,6-dimethylphenyl isocyanide). In turn, the chloride was replaced by cyanide giving Ir(N=C)2(RNC)(CN). The X-ray structures for two of the complexes show that the trans-pyridyl/cis-phenyl geometry of the parent dimer is preserved, with the ancillary ligands positioned trans to the cyclometalated phenyls. The cyano complexes all display strong blue photoluminescence in ambient, deoxygenated solutions with the first lambdamax ranging from 441 to 458 nm, quantum yields spanning 0.60 to 0.75, and luminescent lifetimes of 12.0-21.4 mus. A lack of solvatochromism and highly structured emission indicate that the lowest energy excited state is triplet ligand centered with some admixture of singlet metal-to-ligand charge-transfer character.
Dedeian
Kenneth
K
Army Research Laboratory, 2800 Powder Mill Road, Adelphi, Maryland 20783, USA.
Shi
Jianmin
J
Forsythe
Eric
E
Morton
David C
DC
Zavalij
Peter Y
PY
D018360:Crystallography, X-Ray; D003486:Cyanides / Q000737:chemistry*; D004563:Electrochemistry; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D003486:Cyanides; D008024:Ligands; D009942:Organometallic Compounds; D007495:Iridium