Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M3Se74+(M = Mo, W) with Noninnocento‐Phenanthroline and Se22–Ligands

Gushchin, Artem L.; Sokolov, Maxim N.; Peresypkina, Eugenia V.; Вировец, А. В.; Kozlova, S. G.; Zakharchuk, N. F.; Fedin, Vladimir P.

doi:10.1002/ejic.200800070

Cited by 21 publications

(13 citation statements)

References 25 publications

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“…[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.…”

Section: Resultssupporting

confidence: 71%

“…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…”

Section: Scheme 2 Synthetic Pathway For Complexes 5 -7mentioning

confidence: 99%

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Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters

et al. 2015

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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.

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Section: Resultssupporting

confidence: 71%

Section: Scheme 2 Synthetic Pathway For Complexes 5 -7mentioning

confidence: 99%

Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters

et al. 2015

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“…Recently, Sokolov et al have reported the crystal structure of a {Mo 3 S 7 } 4+ cluster with all outer positions occupied by phenanthroline ligands. This [Mo 3 Se 7 (o Phen) 3 ] 3+ complex was pre pared by reacting the {Mo 3 Se 7 Br 4 } n coordination poly mer with an excess amount of o Phen in melt at 250°C[14]. This procedure can not be extended for the ob tention of the partially substituted o phenanthroline product and we decided to investigate solution routes aimed to isolate a partially substituted product.…”

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confidence: 99%

First heteroleptic Mo3S7 clusters containing non-innocent phenanthroline ligands

et al. 2012

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“…[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.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

et al. 2015

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Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M₃Se₇⁴⁺(M = Mo, W) with Noninnocento‐Phenanthroline and Se₂^2–Ligands

Cited by 21 publications

References 25 publications

Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters

Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters

First heteroleptic Mo3S7 clusters containing non-innocent phenanthroline ligands

Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

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Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M3Se74+(M = Mo, W) with Noninnocento‐Phenanthroline and Se22–Ligands

Cited by 21 publications

References 25 publications

Synthesis and optical power limiting properties of heteroleptic Mo3S7 clusters

Synthesis and optical power limiting properties of heteroleptic Mo3S7 clusters

First heteroleptic Mo3S7 clusters containing non-innocent phenanthroline ligands

Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

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Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M₃Se₇⁴⁺(M = Mo, W) with Noninnocento‐Phenanthroline and Se₂^2–Ligands

Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters

Synthesis and optical power limiting properties of heteroleptic Mo₃S₇ clusters