The mixed metal cluster (n-Bu4N)2[MoCu3OS3(NCS)3]: the first example of a nest-shaped compound with large third-order polarizability and optical limiting effect

Synthesis, crystal structures and third-order nonlinear optical properties of a new family of double incomplete cubane-like clusters [(η5-C5Me5)2Mo2(μ3-S)3SCu2X(μ-X)]2 (X=Cl−, Br−, SCN−) and cubane-like clusters [(η5-C5Me5)2Mo2(μ3-S)4(CuX)2] (X=Br−, SCN−, CN−)

“…Table 4 lists the c values of 2-5, 7, [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 3 S(CuCl) 2 ] and some reported NLO materials for comparison. The c values of 2-5, 7 and [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 3 S(CuCl) 2 ] are comparable to those of the Mo/S/Cu clusters [32,51,[53][54][55], better than those observed in C 60 and C 70 [56], organometallic compounds and their films like TiOPc [57,58]. It is noticed that the c values of the single cubane-like clusters ([(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 3 S(CuCl) 2 ], 3, 5, and 7) are 2-4 times larger, while those of the double incomplete cubane-like Table 2 Selected bond lengths (Å ) and angles (°) for 3 AE 0.5CH 2 Cl 2 , 5 and 7 AE CH 2 Cl 2 a 3 AE 0.5CH 2 Cl 2 5 7 AE CH 2 Cl 2 clusters (2 and 4) are nearly 8 times larger than that of their precursor [(g 5 -C 5 Me 5 ) 2 Mo 2 (l-S) 2 S 2 ].…”

“…Some of these clusters exhibited good third-order nonlinear optical (NLO) properties in solution [16,26,[30][31][32]36,37,39]. In order to expand the chemistry of Mo(W)/Cu/S clusters and screen out clusters with better NLO performances, we have became to adopt other Mo(W)/S precursors including 1 [41][42][43].…”

“…On the other hand, we have been interested in the synthesis of Mo(W)/Cu/S clusters derived from [MO 4Àn S n ] 2À and [(g 5 -C 5 Me 5 )MS 3 ] À (M = Mo, W) [13,14,[16][17][18][19][20][21][22][23][24][25][26][27][30][31][32]39]. Some of these clusters exhibited good third-order nonlinear optical (NLO) properties in solution [16,26,[30][31][32]36,37,39].…”

“…The reactions of thiomolybdates and thiotungstates [MO 4Àn S n ] 2À and [(g 5 -C 5 Me 5 )MS 3 ] À (M = Mo, W) with copper(I) salts have been extensively investigated due to their rich chemistry , and their relations to biological systems [1,5,6,28,29], and electro/photonic materials [11,15,16,24,26,[30][31][32][33][34][35][36][37][38][39]. However, only a few reactions are involved in the utilization of the disulfido-bridged dimolybdenum clusters [Cp 0 2 Mo 2 S 4 ] (Cp 0 = g 5 -C 5 H 5 , g 5 -C 5 H 4 Me or g 5 -C 5 Me 5 ) [40,41].…”

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

“…There are several potential mechanisms that have been discussed and applied so far to define and describe the observed optical nonlinearity in heterothiometallic clusters. ,,− ,,,− As said before, studies on these clusters demonstrated that the skeleton units, peripheral ligands, different central and skeletal metal atoms, as well as structural geometry have a major influence on their optical nonlinearities. As a result, the relative contributions of different NLO mechanisms change consequently with the skeletal types of clusters.…”