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Dithiolene dimetallic molybdenum(V) complexes displaying intraligand charge transfer (ILCT) emission
David Recatalá1, Artem L Gushchin, Rosa Llusar
1Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castelló, Spain. rosa.llusar@uji.es.
Dalton Transactions (Cambridge, England : 2003)
|June 27, 2013
Summary
New molybdenum-based complexes featuring dithiolene ligands exhibit tunable photoluminescence properties. These complexes, including a tetrametallic rhenium-molybdenum structure and a tin analog, show potential for applications in light-emitting technologies.
Area of Science:
- Coordination Chemistry
- Materials Science
- Photophysics
Background:
- Bifunctional dithiolene ligands are versatile building blocks in coordination chemistry.
- Molybdenum-sulfur clusters are of interest for their unique electronic and catalytic properties.
- Understanding structure-property relationships in metal complexes is crucial for developing new materials.
Purpose of the Study:
- To synthesize and characterize novel molybdenum-dimer complexes with bifunctional dithiolene ligands.
- To investigate the structural and photoluminescent properties of these complexes, including a tetrametallic derivative and a tin analogue.
- To explore the impact of metal coordination on the luminescence behavior of the dithiolene ligand system.
Main Methods:
- Synthesis of molybdenum-dimer complexes ([Mo2O2(μ-S)2(BPyDTS2)2](2-)) and a tetrametallic complex ([Mo2O2(μ-S)2(BPyDTS2)2{Re(CO)3Cl}2](2-)).
- Preparation of a monomeric tin complex ((CH3)2Sn(BPyDTS2)) for comparative studies.
- Structural characterization using X-ray crystallography and investigation of luminescence properties in acetonitrile, supported by quantum mechanical calculations.
Main Results:
- The molybdenum dimer complex exhibits photoluminescence in the 600-800 nm region, with a maximum at 628 nm and a quantum yield of 0.092, attributed to an intraligand charge transfer (ILCT) transition.
- Coordination of rhenium fragments to the molybdenum dimer slightly reduces the quantum yield but does not significantly alter the emission spectrum.
- The tin complex displays similar emission characteristics to the molybdenum complexes, supporting the ILCT assignment and indicating ligand-based luminescence.
Conclusions:
- The synthesized molybdenum-dimer and tetrametallic complexes, along with the tin analogue, demonstrate tunable photoluminescence based on an ILCT mechanism.
- The study highlights the influence of metal coordination on the photophysical properties of dithiolene ligands.
- These findings provide insights into the design of novel luminescent materials based on metal-sulfur complexes.
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