The First Assembly of a Nest-Shaped Heterothiometallic Cluster and a Polyoxometalate Anion − Synthesis, Characterization, and Strong Third-Order Nonlinear Optical Response

Abstract

Two heterothiometallic cluster compounds [MOS 3 Cu 3 (4-pic) 6 ]·0.5[M 2 O 7 ] (M = Mo 1, W 2) having a cationic cluster skeleton and a polyoxometalate cluster anion, as well as two other clusters [MOS 3 Cu 3 (4-pic) 6 ]·[BF 4 ] (M = Mo 3, W 4) have been synthesized for nonlinear optics studies. Single-crystal X-ray diffraction data show that cluster 1 adopts a very interesting arrangement with a cationic nest-shaped cluster skeleton and a polyoxomolybdenum cluster anion. This is the first time that such a skeleton has been found for an Mo/S/Cu heterothiometallic cluster compound and it represents a distinct structural type as compared to the analogous nestshaped clusters seen with a neutral or an anionic skeleton.

Formation of new organometallic W/Cu/S clusters from reactions of [{(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 with donor ligands. Crystal structures and optical limiting properties of [(η5-C5Me5)WS3Cu3(Py)6](PF6)2, [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6), and [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2

“…The oxidation states for W and Cu atoms are retained as +6, and +1, respectively. This structure is closely related to [MOS 3 Cu 3 -(4-pic) 6 ][Mo 2 O 7 ] 0.5 and [MOS 3 Cu 3 (4-pic) 6 ](BF 4 ) (M = Mo, W, 4-pic = 4-picoline) [14]. The [(g 5 -C 5 Me 5 )WS 3 ] À anion of 2 has a slightly distorted three-legged piano stool structure.…”

Depth Profiling (ICP-MS) Study of Trace Metal ‘Grains’ in Solid Asphaltenes

“…Therefore, treatment of asphaltenes in terms of demetallization and in other processes could change on this basis. Organometallic structures of similar nature are well known, and of increasing interest in various areas of chemistry [7][8][9][10][11][12][13][14]. The existence of such metal 'grains' at random points in the asphaltene matrix is unexplored and could open up a new area of study and interesting possibilities, for example using the metal-containing asphaltene as in situ catalysts for workup procedures [15].…”

Synthesis, structural characterization and third-order non-linear optical property of new three-dimensional metal-organic polymer [Fe2(μ10-btc)0.5(μ2-ox)0.5(μ2-O)1.5]n

“…Among the three absorption peaks, the two in the ultraviolet region indicate the presence of metal-ligands transfer transitions, and the wide peak in the visible region shows the presence of charge-transfer transitions. It also shows that the polymer has potential as optical limiter [22].…”