Dithiolene dimetallic molybdenum(V) complexes displaying intraligand charge transfer (ILCT) emission
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Other documents of the author: Recatalá Ferrandis, David; Gushchin, Artem L.; Llusar, Rosa; Galindo, Francisco; Brylev, Konstantin A.; Ryzhikov, Maxim R.; Kitamura, Noboru
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http://dx.doi.org/10.1039/c3dt51102b |
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Title
Dithiolene dimetallic molybdenum(V) complexes displaying intraligand charge transfer (ILCT) emissionAuthor (s)
Date
2013Publisher
Royal Society of ChemistryType
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/publishedVersionSubject
Abstract
Bifunctional dithiolene ligands have been coordinated to the MoV(O)(μ-S2)MoV(O) unit to afford
[Mo2O2(μ-S)2(BPyDTS2)2]2− (12−) (BPyDTS2 (2-bis-(2-pyridyl)methylene-1,3-dithiolene) dianions. Reaction
of the 12− ... [+]
Bifunctional dithiolene ligands have been coordinated to the MoV(O)(μ-S2)MoV(O) unit to afford
[Mo2O2(μ-S)2(BPyDTS2)2]2− (12−) (BPyDTS2 (2-bis-(2-pyridyl)methylene-1,3-dithiolene) dianions. Reaction
of the 12− molybdenum dimer with pentacarbonylchlorothenium(I) affords a tetrametallic complex of
formula [Mo2O2(μ-S)2(BPyDTS2)2{Re(CO)3Cl}2]2− (22−). The monomeric (CH3)2Sn(BPyDTS2) (3) tin complex
has also been prepared for comparative purposes. In the structure of (Et4N)2[1], the two metal atoms are
in a square pyramidal coordination environment defined by two bridging sulfur atoms, one terminal
oxygen atom and the two sulfur atoms of the bifunctional dithiolene ligand. This arrangement leaves
two nitrogen atoms on each side which coordinate to two Re atoms in the 22− tetrametallic complex.
Compound 3 has a distorted tetrahedral structure defined by two carbon atoms of the methyl groups
and two sulfur atoms of the dithiolene ligand. The luminescence properties of all three complexes in
acetonitrile have been investigated. Detailed studies supported on quantum mechanical calculations
revealed that complex 12− shows photoluminescence in the 600–800 nm region with a maximum wavelength
of 628 nm and an emission quantum yield of 0.092, associated with an intraligand charge transfer
(ILCT) transition. Coordination of two Re(CO)3Cl fragments to 12− to afford 22− does not affect the emission
spectrum and shape although it decreases the quantum yield, approximately by a factor of 4.6. Compound
3 exhibits a similar emission spectrum to those of the complexes 12− and 22− in good agreement
with the ILCT assignment. The quantum yield of 3 lies between that of the 12− and 22− complexes. [-]
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Dalton Transactions. 2013, 42Rights
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