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Updated: Dec 18, 2025

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
More efficient spin-orbit coupling: adjusting the ligand field strength to the second metal ion in asymmetric
Zhaoran Hao1, Kai Zhang, Kuan Chen
1College of Chemistry, Key Lab of Environment-Friendly Chemistry and Application in Ministry of Education, Xiangtan University, Xiangtan 411105, China. liuyu03b@126.com.
Abstract:
Two types of asymmetric binuclear platinum(ii) complexes (Pt-1 and Pt-3) bearing bridging ligands of 2-(2,4-difluorophenyl)-5-(pyridin-2-yl)pyridine and 2-(2,4-difluorophenyl)-4-(pyridin-2-yl)pyridine as well as their corresponding mononuclear counterparts (Pt-2, Pt-4, and Pt-5) were synthesized and characterized. Different chelating constructions of the second platinum(ii) ions and the bridging ligands in Pt-1 and Pt-3 gave rise to two kinds of electron-transition pathway during their photophysical processes. The meta-/para-carbon of nitrogen on the center pyridyl segments set different levels of ligand field strength to the second platinum(ii) ions, lowering their occupied d orbital to varying degrees. Pt-1 showed an enhanced spin-orbit coupling (SOC), caused by the additional metal component through direct orbital hybridization at higher states, where the fixed molecular skeleton induced by the additional metal-ligand bonding also helped to suppress molecular distortion in the excited state, ensuring a high quantum yield (Φ, 0.89 in toluene), which is among the best results in bimetallic complexes. While the second platinum(ii) ion in Pt-3 seemed to make no contribution to the radiative transition, and only contributed to the HOMO, it provided a benefit by enlarging the conjugate system. Solution-processed organic lighting emitting devices (OLEDs) fabricated with the bimetallic Pt-1 emitter achieved superior efficiencies and up to 21% external quantum efficiency (EQE) in the Kelly-green region.
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