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Pincer‐Type Platinum(II) Complexes Containing N‐Heterocyclic Carbene (NHC) Ligand: Structures,Photophysical and Anion‐Binding Properties,and Anticancer Activities
Authors:Dr Kai Li  Dr Taotao Zou  Prof?Dr Yong Chen  Dr Xiangguo Guan  Prof?Dr Chi‐Ming Che
Institution:1. State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, HKU‐CAS Joint Laboratory on New Materials and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (P.R. China), Fax: (+852)?2915‐5176;2. HKU Shenzhen Institute of Research and Innovation, Shenzhen 518053 (P.R. China);3. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China)
Abstract:Two classes of pincer‐type PtII complexes containing tridentate N‐donor ligands ( 1 – 8 ) or C‐deprotonated N^C^N ligands derived from 1,3‐di(2‐pyridyl)benzene ( 10 – 13 ) and auxiliary N‐heterocyclic carbene (NHC) ligand were synthesized. Pt(trpy)(NHC)]2+ complexes 1 – 5 display green phosphorescence in CH2Cl2 (Φ: 1.1–5.3 %; τ: 0.3–1.0 μs) at room temperature. Moderate‐to‐intense emissions are observed for 1 – 7 in glassy solutions at 77 K and for 1 – 6 in the solid state. The Pt(N^C^N)(NHC)]+ complexes 10 – 13 display strong green phosphorescence with quantum yields up to 65 % in CHCl3. The reactions of 1 with a wide variety of anions were examined in various solvents. The tridentate N‐donor ligand of 1 undergoes displacement reaction with CN? in protic solvents. Similar displacement of the N^C^N ligand by CN? has been observed for 10 , leading to a luminescence “switch‐off” response. The water‐soluble 7 containing anthracenyl‐functionalized NHC ligand acts as a light “switch‐on” sensor for the detection of CN? ion with high selectivity. The in vitro cytotoxicity of the PtII complexes towards HeLa cells has been evaluated. Complex 12 showed high cytotoxicity with IC50 value of 0.46 μM , whereas 1 – 4 and 6 – 8 are less cytotoxic. The cellular localization of the strongly luminescent complex 12 traced by using emission microscopy revealed that it mainly localizes in the cytoplasmic structures rather than in the nucleus. This complex can induce mitochondria dysfunction and subsequent cell death.
Keywords:anions  cancer  carbenes  cyanides  luminescence  platinum
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