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Room‐Temperature Phosphorescence and Energy Transfer in Luminescent Multinuclear Platinum( II ) Complexes of Branched Alkynyls
Author(s) -
Tao ChiHang,
Zhu Nianyong,
Yam Vivian WingWah
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400888
Subject(s) - phosphorescence , platinum , energy transfer , luminescence , chemistry , photochemistry , materials science , optoelectronics , organic chemistry , physics , chemical physics , fluorescence , optics , catalysis
A series of luminescent branched platinum( II ) alkynyl complexes, [1,3,5‐{RCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 3 C 6 H 3 ] (R=C 6 H 5 , C 6 H 4 OMe, C 6 H 4 Me, C 6 H 4 CF 3 , C 5 H 4 N, C 6 H 4 SAc, 1‐napthyl (Np), 1‐pyrenyl (Pyr), 1‐anthryl‐8‐ethynyl (HCCAn)), [1,3‐{PyrCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 2 ‐5‐{( i Pr) 3 SiCC}C 6 H 3 ], and [1,3‐{PyrCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 2 ‐5‐(HCC)C 6 H 3 ], was successfully synthesized by using the precursors [1,3,5‐{Cl(PEt 3 ) 2 PtCCC 6 H 4 CC} 3 C 6 H 3 ] or [1,3‐{Cl(PEt 3 ) 2 PtCCC 6 H 4 CC} 2 ‐5‐{( i Pr) 3 SiCC}C 6 H 3 ]. The X‐ray crystal structures of [1,3,5‐{MeOC 6 H 4 CC(PEt 3 ) 2 PtCCC 6 H 4 CC} 3 C 6 H 3 ] and [1,8‐{Cl(PEt 3 ) 2 PtCC} 2 An] have been determined. These complexes were found to show long‐lived emission in both solution and solid‐state phases at room temperature. The emission origin of the branched complexes [1,3,5‐ {RCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 3 C 6 H 3 ] with R=C 6 H 5 , C 6 H 4 OMe, C 6 H 4 Me, C 6 H 4 CF 3 , C 5 H 4 N, and C 6 H 4 SAc was tentatively assigned to be derived from triplet states of predominantly intraligand (IL) character with some mixing of metal‐to‐ligand charge‐transfer (MLCT) (dπ(Pt)→π*(CCR)) character, while the emission origin of the branched complexes with polyaromatic alkynyl ligands, [1,3,5‐{RCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 3 C 6 H 3 ] with R=Np, Pyr, or HCCAn, [1,3‐{PyrCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 2 ‐5‐{( i Pr) 3 SiCC}C 6 H 3 ], [1,3‐{PyrCC(PEt 3 ) 2 PtCCC 6 H 4 CC} 2 ‐5‐(HCC)C 6 H 3 ], and [1,8‐{Cl(PEt 3 ) 2 PtCC} 2 An], was tentatively assigned to be derived from the predominantly 3 IL states of the respective polyaromatic alkynyl ligands, mixed with some 3 MLCT (dπ(Pt)→π*(CCR)) character. By incorporating different alkynyl ligands into the periphery of these branched complexes, one could readily tune the nature of the lowest energy emissive state and the direction of the excitation energy transfer.