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Structural and photophysical study on heterobimetallic complexes with d8-d10 interactions supported by carborane ligands: Theoretical analysis of the emissive behaviour

AutorCrespo, Olga ; Gimeno, M. Concepción ; Laguna, Antonio ; Lehtonen, Olli; Ospino, Isaura; Pyykkö, Pekka; Villacampa, M. Dolores
Palabras claveCarboranes
Metal–metal interactions
Luminescence
Heterometallic complexes
Transition metals
Fecha de publicación2014
EditorWiley-VCH
CitaciónChemistry - A European Journal 20(11): 3120-3127 (2014)
ResumenHeterobimetallic complexes of formula [M{(PPh2) 2C2B9H10}(S2C 2B10H10)M'(PPh3)] (M=Pd, Pt; M'=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H 10}(S2C2B10H10) Au(PPh3)] were obtained from the reaction of [M{(PPh 2)2C2B10H10}(S 2C2B10H10)] (M=Pd, Pt) with [M'(PPh3)]+ (M'=Au, Ag, Cu) or by one-pot synthesis from [(SH)2C2B10H10], (PPh 2)2C2B10H10, NiCl 2×6 H2O, and [Au(PPh3)]+. They display d8-d10 intermetallic interactions and emit red light in the solid state at 77aK. Theoretical studies on [M{(PPh 2)2C2B9H10}(S 2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to->P2-M-S2> (ML') charge-transfer (LML'CT) transitions for M=Pt and to metal (M)-to->P2-M-S 2> (ML') charge-transfer (MML′CT) transitions for M=Ni, Pd. A family of red emitters of formula [M{(PPh2)2C 2B9H10}(S2C2B 10H10)M′(PPh3)] (M=Pd, Pt; M′=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H 10}(S2C2B10H10) Au(PPh3)] (see figure) was synthesised. Theoretical studies on [M{(PPh2)2C2B9H10}(S 2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to->P2-M-S2> group (ML′) charge-transfer (LML′CT) transitions for M=Pt and to metal (M)-to->P2-M-S2> group (ML′) charge-transfer (MML′CT) transitions for M=Ni, Pd. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
URIhttp://hdl.handle.net/10261/111618
DOI10.1002/chem.201303735
Identificadoresdoi: 10.1002/chem.201303735
issn: 0947-6539
e-issn: 1521-3765
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