Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters

Abstract

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) (1), Mo3S7Br4(dmbpy) (2), Mo3S7Br4(bpy) (3), and Mo3S7Br4(phen) (4). 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 (5, dnbpy = 4,4'-dinonyl-2,2'-bipyridine), Mo3S7(dcmbpy)(dmit)2 (6, dcmbpy = 4,4′-dimethoxycarbonyl-2,2′-bipyridine), and Mo3S7(dcbpy)(dmit)2 (7, dcbpy = 2,2'-bipyridine-4,4'-dicarboxylic acid). The optical limiting properties of complexes 1 -7 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 -system, complexes 1 -4, with general formula Mo3S7X4(diimine), (X = Cl, Br), were compared to clusters 5 -7, 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 1 -7 are efficient optical limiters (eff > 0) with threshold limiting fluence F15% decreasing on proceeding from dinuclear to trinuclear clusters and, generally, on extending the -system.

New Methods for the Functionalization of Polymer Matrices with Thiomolybdate Clusters Applied for Hydrogen Evolution Reaction Catalysis

“…These bands are characteristic for [Mo 3 S 13 ] 2À -based disulfide vibrations [36,37] and are known to change significantly upon structural changes of the cluster (e.g., ligand exchange or degradation). [19,[38][39][40] Also, UV-vis spectroscopy of P1 revealed spectral features in the 300À450 nm range, which are in line with [Mo 3 S 13 ] 2À -based signals. [19] These data suggest that the general [Mo 3 ] structure of the cluster is retained in P1.…”

Facile synthesis, crystal growth, characterization and computational study of new pyridine‐based halogenated hydrazones: Unveiling the stabilization behavior in terms of noncovalent interactions

“…Over the past two decades, organic conjugated molecules have been widely used as advanced materials because of their fascinating large NLO response and structural tenability . They have been extensively applied in the fields of photonics, optoelectronics in all‐optical switching, data storage and optical power limiting .…”

Femtosecond nonlinear absorption and optical limiting action in nanoplatelet CuFe2O4-decorated rGO nanocomposites

“…Such fs lasers, with capacity of delivering high intensities at short intervals of time, are capable of damaging the optical components, and therefore, numerous attempts are being made in preventing these laser-based accidents damaging the human eyes and precious sensors. The desideratum of ideal optical power limiters to delicate optical components (including the human eyes) with a low damage threshold due to deliberate or unintentional exposure to these high power lasers is one of the ultimate challenges for the optics community [8][9][10][11]. Consequently, the development of optical limiting devices has shown tremendous advancement due to its possible utility in photonic application like laser safety devices, optical shutter, pulse shaping and light stabilizing sources [12][13][14].…”

“…Earlier reports showcase that the combination of rGO with CuFe 2 O 4 can yield potential systems with strong nonlinearity [36]. Also ferrites are investigated in different optoelectronic applications as it possess the advantages of (a) owning 3d 10 4 s 1 configuration in the valence shell, (b) available at low cost and (c) environmentally benign [37][38][39]. So using the different intensities (I o = 245, 490 and 735 MW/cm 2 ) of Ti:Sapphire (150 fs, 800 nm and 80 MHz) laser pulses, NLO activities of a series of CuFe 2 O 4 -rGO nanocomposites were measured.…”