A luminescent Pt(II) complex with a terpyridine-like ligand involving a six-membered chelate ring |
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Authors: | Hu Yi-Zhen Wilson Michael H Zong Ruifa Bonnefous Celine McMillin David R Thummel Randolph P |
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Institution: | Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana, 47907-2084, USA. |
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Abstract: | The ligand 2-(8'-quinolinyl)-1,10-phenanthroline (1) was prepared in 79% yield by the Friedlander condensation of 8-amino-7-quinolinecarbaldehyde and 8-acetylquinoline. The complex Pt(1)Cl]+ was prepared and compared with the isomeric 2-(2'-quinolinyl)-1,10-phenanthroline (2) complex. An X-ray analysis indicated that the six-membered chelate ring in the tridentate complex resulted in a relief of angle strain as well as some non-planarity in the bound ligand 1. The control system for photophysical studies is Pt3Cl]+ where denotes 2-(2'-pyridyl)-1,10-phenanthroline. Relative to the complex of 3, in dichloromethane solution Pt(1)Cl]+ exhibits noticeably higher energy charge-transfer absorption but slightly lower energy emission. The gap between the onset of absorption and emission is larger because the emission from Pt(1)Cl]+ originates from a triplet excited state with substantial intra-ligand character. At room temperature in deoxygenated dichloromethane, Pt(1)Cl]+ has an excited-state lifetime of 310 ns vs. 230 ns for Pt(1)Cl]+. Within the series, Pt(1)Cl]+ also exhibits the largest activation barrier for thermally induced quenching at 2730 cm(-1) in fluid dichloromethane solution. However, the barrier is only about 50% larger than that found for Pt(1)Cl]+. There is reduced ring strain in Pt(1)Cl]+, but inter-ligand steric interactions weaken the ligand field. |
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