First heteroleptic Mo3S7 clusters containing non-innocent phenanthroline ligands

Abstract

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Synthesis and optical power limiting properties of heteroleptic Mo3S7 clusters

“…[18][19][20][21][22][23][24][25] Intracluster metal-metal and metal-sulfur bond distances are consistent with those for an oxidation state of +4 for the metal, and the presence of single metal-metal bonds (see Table 1). [18][19][20][21][22][23][24][25] In addition to the crystal structure determinations, the identities of complexes (Bu4N) [1 -4] were confirmed by mass spectrometry. for the synthesis of complexes 5 -7 is summarized in Scheme 2.…”

“…9 It is well-known that in [Mo3(µ3-S)(µ-S2)3] 4+ units the sulfur atoms that lie in the axial plane are slightly electrophilic, and consequently can interact with nucleophilic anions, such as the chloride/bromide ligands replaced by the diimine or dithiolene ligands during the substitution reaction. [18][19][20][21][22][23][24][25] Consequently, tetra-n-butylammonium salts of…”

Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

“…[3][4][5][6] Interestingly, the reaction of [Mo 3 (μ 3 -S)(μ-S 2 ) 3 Br 6 ] 2with an excess of a diimine ligand selectively replaces two bromido ligands on one metal atom to afford neutral Mo 3 S 7 Br 4 (diimine) complexes in high yields. [11,12] To extend the scope of this synthetic route, we employed other metal precursors, that is, [Mo 3 (μ 3 -S)(μ-S 2 ) 3 Cl 6 ] 2-, and other 1,10-phenanthroline derivatives. The synthetic approaches used for the synthesis of the target molecules are shown in Scheme 1.…”

“…[11,12,[19][20][21] It is well established that axial sulfur atoms in group-six M 3 S 7 cluster chalcogenides possess an electrophilic character and interact with anions, such as halides, perchlorates, or sulfides. Nevertheless, sonication of the powder in the presence of dichloromethane and an excess of a tetrabutylammonium halide salt (either nBu 4 NBr or nBu 4 NCl) led to the complete dissolution of the cluster species.…”

Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

“…[5] Examples of group 6 complexes featuring N-donor ligands such as [M(Mebipy) 3 ] and [M(tpy) 2 ] (M = Cr, Mo and W; Mebipy = 4,4Ј-dimethyl-2,2Ј-bipyridine and tpy = 2,2Ј,6Ј,2ЈЈ-terpyridine) have been provided by Wieghardt's group. [6,7] However, coordination chemistry of such noninnocent ligands with chalcogenide clusters is rather limited, with reported examples including coordination of bipyridine or phenanthroline to V 3 S 7 , [8] Mo 3 S 4 , [9,10] Mo 3 Q 7 (Q = S, Se), [11][12][13] M(μ 3 -S) 3 Cu 3 (M = Mo, W), [14] and Mo 2 S 2 O 2 cluster units. [15] It is expected that "electron sink" properties of the chalcogenide cluster cores coupled with their structural and electronic diversity may lead to novel and potentially important properties.…”