Electron density distribution, polarizability and bonding in the octahedral clusters [Mo6S8(CN)6]6−, [Re6S8(CN)6]4− and Rh6(CO)16

Baranovski, V. I.; Korol’kov, D. V.

doi:10.1016/j.poly.2004.03.013

Cited by 13 publications

(10 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The temperature-dependent photophysics of the [Re 6 Q 8 ] 2 + series has been extensively characterized experimentally. [78,79,83] Hartree-Fock, [78] density-functional, [78,84,85] Tamm-Dankoff CI, [86] and SW-Xa calculations [90] are all available for the rhenium chalcogenide clusters. Time-dependent DFT calculations are reported for [Re 6 S 8 Cl 6 ] 4À , and a spectroscopically calibrated functional,…”

mentioning

confidence: 99%

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Gray

2009

Chemistry A European J

View full text Add to dashboard Cite

Same but different: DFT calculations on hexanuclear tungsten(II) halide clusters [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I) indicate a breakdown in the isoelectronic analogy between themselves and the isostructural rhenium(III) chalcogenide clusters [Re(6)S(8)X(6)](4-) (see figure).The hexanuclear tungsten(II) halide clusters and the sulfido-halide clusters of rhenium(III) are subsets of a broad system of 24-electron metal-metal bonded assemblies that share a common structure. Tungsten(II) halide clusters and rhenium(III) sulfide clusters luminesce from triplet excited states upon ultraviolet or visible excitation; emission from both cluster series has been extensively characterized elsewhere. Reported here are density-functional theory studies of the nine permutations of [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I). Ground-state properties including geometries, harmonic vibrational frequencies, and orbital energy-level diagrams, have been calculated. Comparison is made to the sulfide clusters of rhenium(III), of which [Re(6)S(8)Cl(6)](4-) is representative. [W(6)X(8)X'(6)](2-) and [Re(6)S(8)Cl(6)](4-) possess disparate electronic structures owing to the greater covalency of the metal-sulfur bond and hence of the [Re(6)S(8)](2+) core. Low-lying virtual orbitals are raised in energy in [Re(6)S(8)Cl(6)](4-) with the result that the LUMO+7 (or LUMO+8 in some cases) of tungsten(II) halide clusters is the LUMO of [Re(6)S(8)Cl(6)](4-) species. An inversion of the HOMO and HOMO-1 between the two cluster series also occurs. Time-dependent density-functional calculations using asymptotically correct functionals do not recapture the experimentally observed periodic trend in [W(6)X(14)](2-) luminescence (E(em) increasing in the order [W(6)Cl(14)](2-) < [W(6)Br(14)](2-) < [W(6)I(14)](2-)), predicting instead that emission energies decrease with incorporation of the heavier halides. This circumstance is either a gross failure of the time-dependent formalism of DFT or it indicates extensive multistate emission in [W(6)X(8)X'(6)](2-) clusters. The inapplicability of isoelectronic analogies between clusters of Group 6 and Group 7 is emphasized.

show abstract

mentioning

confidence: 99%

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Gray

2009

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…These changes are just the same as those induced by the formation of the adduct 2 from [Mo 6 S 8 (CN) 6 ] 6À and Cr(CO) 5 . So the results of [7] and of this work taken together gave the sound ground for the explanation of the structural changes in the adducts as a consequence of the electrostatic effects and of the pseudo-Jhan-Teller effect.…”

mentioning

confidence: 64%

“…Our study of the [Mo 6 S 8 (CN) 6 ] 6À cluster [6,7] showed that in this compound the electron density is concentrated on the Mo-Mo bonds and on the faces of the Mo 6 polyhedron. Moreover, there is uniformly distributed electron density of 0.06 e/a.u.…”

mentioning

confidence: 83%

“…It was shown earlier [7] that in the uniform electric field, there are significant changes in the geometry parameters as well as noticeable charge redistribution in the complex. These changes are just the same as those induced by the formation of the adduct 2 from [Mo 6 S 8 (CN) 6 ] 6À and Cr(CO) 5 .…”

mentioning

confidence: 85%

“…This model suggests that such system is very polarizable. Indeed, the calculated [7] polarizabilities of Mo 6 S 8 (47 Å 3 ) and [Mo 6 S 8 (CN) 6 ] 6À (57 Å 3 ) clusters are very high. It is reasonable to assume that deformation of the Mo 6 core is a consequence of the shift of the positively charged Mo d+ cores under the influence of the charged CO and L groups in the Cr(CO) 5 L fragments.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Quantum chemical study of the addition effect on the geometry of the [Mo6S8(CN)6]6− cluster

Baranovski

Tunik

Korol’kov

2005

Inorganic Chemistry Communications

View full text Add to dashboard Cite

Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re_6−xMo_xSe₈(CN)₆]ⁿ⁻

Muravieva

Gayfulin

Prestipino

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

Influence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)6 octahedral clusters. The discrete anionic clusters [Re6‐xMoxSe8(CN)6]n− (x=2, 3; n=4, 5) were obtained as individual salts. Their isomeric composition and bond‐length distribution were inspected using a combination of single‐crystal X‐ray structure analysis, NMR, EXAFS, and DFT calculations.

show abstract

Electron density distribution, polarizability and bonding in the octahedral clusters [Mo6S8(CN)6]6−, [Re6S8(CN)6]4− and Rh6(CO)16

Cited by 13 publications

References 16 publications

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Quantum chemical study of the addition effect on the geometry of the [Mo6S8(CN)6]6− cluster

Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re_6−xMo_xSe₈(CN)₆]ⁿ⁻

Contact Info

Product

Resources

About

Electron density distribution, polarizability and bonding in the octahedral clusters [Mo6S8(CN)6]6−, [Re6S8(CN)6]4− and Rh6(CO)16

Cited by 13 publications

References 16 publications

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Quantum chemical study of the addition effect on the geometry of the [Mo6S8(CN)6]6− cluster

Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re6−xMoxSe8(CN)6]n−

Contact Info

Product

Resources

About

Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re_6−xMo_xSe₈(CN)₆]ⁿ⁻