Synthesis and optical power limiting properties of heteroleptic Mo3S7 clusters.

Substitution of the halide ligands in (Bu4N)2[Mo3S7X6] (X = Cl, Br) by diimine ligands, such as 4,4'-dimethyl-2,2'-bipyridine (dmbpy), 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen), affords the neutral heteroleptic clusters Mo3S7Cl4(dmbpy) (), Mo3S7Br4(dmbpy) (), Mo3S7Br4(bpy) (), and Mo3S7Br4(phen) (). Further substitution of the halide ligands in Mo3S7Br4(diimine) clusters by dmit (1,3-dithiole-2-thione-4,5-dithiolate) allows the preparation of the mixed diimine-dithiolene neutral cluster complexes Mo3S7(dnbpy)(dmit)2 (, dnbpy = 4,4'-dinonyl-2,2'-bipyridine), Mo3S7(dcmbpy)(dmit)2 (, dcmbpy = 4,4'-dimethoxycarbonyl-2,2'-bipyridine), and Mo3S7(dcbpy)(dmit)2 (, dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid). The optical limiting properties of complexes have been assessed by the open-aperture Z-scan technique at 570 nm, employing a nanosecond optical parametric oscillator. In order to investigate the effect of increasing the π-system, complexes , with the general formula Mo3S7X4(diimine), (X = Cl, Br), were compared to clusters , containing the dmit ligand. The influence of the metal content on the optical power limiting properties was also investigated by comparing the trinuclear series of complexes prepared herein with the bis(dithiolene) dinuclear cluster (Et4N)2[Mo2O2S2(BPyDTS2)2], which has been recently prepared by our group. All trinuclear clusters are efficient optical limiters (σeff > σ0) with the threshold limiting fluence F15% decreasing on proceeding from dinuclear to trinuclear clusters and, generally, on extending the π-system.

Photogeneration of hydrogen from water by hybrid molybdenum sulfide clusters immobilized on titania.

Two new hybrid molybdenum(IV) Mo3 S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3 S7 Br6 ](2-) by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3 S7 Br4 (diimino) complexes. Adsorption of the Mo3 S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3 S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.3 V (for 1 mA cm(-2) ) with a turnover frequency as high as 1.4 s(-1) . The nature of the actual active molybdenum sulfide species has been investigated by X-ray photoelectron spectroscopy. In agreement with the electrochemical results, the modified TiO2 nanoparticles show a high photocatalytic activity for H2 production in the presence of Na2 S/Na2 SO3 as a sacrificial electron donor system.

Dithiolene dimetallic molybdenum(V) complexes displaying intraligand charge transfer (ILCT) emission.

Bifunctional dithiolene ligands have been coordinated to the Mo(V)(O)(µ-S2)Mo(V)(O) unit to afford [Mo2O2(µ-S)2(BPyDTS2)2](2-) (1(2-)) (BPyDTS2 (2-bis-(2-pyridyl)methylene-1,3-dithiolene) dianions. Reaction of the 1(2-) molybdenum dimer with pentacarbonylchlorothenium(i) affords a tetrametallic complex of formula [Mo2O2(µ-S)2(BPyDTS2)2{Re(CO)3Cl}2](2-) (2(2-)). 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 2(2-) 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 1(2-) 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 1(2-) to afford 2(2-) 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 1(2-) and 2(2-) in good agreement with the ILCT assignment. The quantum yield of 3 lies between that of the 1(2-) and 2(2-) complexes.