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Structural and Photophysical Study on Heterobimetallic Complexes with d 8 –d 10 Interactions Supported by Carborane Ligands: Theoretical Analysis of the Emissive Behaviour
Author(s) -
Crespo Olga,
Gimeno M. Concepción,
Laguna Antonio,
Lehtonen Olli,
Ospino Isaura,
Pyykkö Pekka,
Villacampa M. Dolores
Publication year - 2014
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.201303735
Subject(s) - chemistry , ligand (biochemistry) , metal , carborane , crystallography , intermetallic , stereochemistry , luminescence , physics , biochemistry , receptor , optoelectronics , organic chemistry , alloy
Heterobimetallic complexes of formula [M{(PPh 2 ) 2 C 2 B 9 H 10 }(S 2 C 2 B 10 H 10 )M′(PPh 3 )] (M=Pd, Pt; M′=Au, Ag, Cu) and [Ni{(PPh 2 ) 2 C 2 B 9 H 10 }(S 2 C 2 B 10 H 10 )Au(PPh 3 )] were obtained from the reaction of [M{(PPh 2 ) 2 C 2 B 10 H 10 }(S 2 C 2 B 10 H 10 )] (M=Pd, Pt) with [M′(PPh 3 )] + (M′=Au, Ag, Cu) or by one‐pot synthesis from [(SH) 2 C 2 B 10 H 10 ], (PPh 2 ) 2 C 2 B 10 H 10 , NiCl 2 ⋅ 6 H 2 O, and [Au(PPh 3 )] + . They display d 8 –d 10 intermetallic interactions and emit red light in the solid state at 77 K. Theoretical studies on [M{(PPh 2 ) 2 C 2 B 9 H 10 }(S 2 C 2 B 10 H 10 )Au(PPh 3 )] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)‐to‐“P 2 ‐M‐S 2 ” (ML′) charge‐transfer (LML′CT) transitions for M=Pt and to metal (M)‐to‐“P 2 ‐M‐S 2 ” (ML′) charge‐transfer (MML′CT) transitions for M=Ni, Pd.