Extended materials based on the [Mo6Cl8]4+ building block bridged by 4,4′-bipyridine

Bain, R. L.; Shriver, Duward F.; Ellis, Donald E

doi:10.1016/s0020-1693(01)00631-4

Cited by 34 publications

(26 citation statements)

References 26 publications

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“…DFT calculations for Cs 2 [Mo 6 Cl 14 ] were conducted assuming the trigonal lattice model with the centrosymmetric space group (P 31c), 2),26),27) as shown in Fig. 1, because we had previously confirmed the presence of centrosymmetry by observing the absence of second-harmonic generation (SHG) from Cs 2 [Mo 6 Cl 14 ] under irradiation by a high-intensity infrared (IR) laser.…”

Section: Methodsmentioning

confidence: 99%

“…1, because we had previously confirmed the presence of centrosymmetry by observing the absence of second-harmonic generation (SHG) from Cs 2 [Mo 6 Cl 14 ] under irradiation by a high-intensity infrared (IR) laser. 26) Hence, relaxation of the lattice parameters and atomic coordinates of Cs 2 [Mo 6 Cl 14 ] was achieved by applying structural constraints so that the space group of the lattice could maintain the P 31c symmetry. The initial structural model for the geometry optimization is summarized in Table S1 in the supporting information.…”

Section: Methodsmentioning

confidence: 99%

“…The most accurate lattice structure was obtained using PBEsol, which could be attributed to PBEsol being specifically designed for yielding accurate jellium surface energies. 39 Figure 3 shows the band structure and total DOS (TDOS) of Cs 2 [Mo 6 Cl 14 ] calculated with the three functionals. Because the energy band structures for the up-and down-spin states are identical, only the up-spin component is shown in the E-k dispersion plots, and the TDOS plotted here is the summation of the up-and down-spin components.…”

Section: Computational Analysesmentioning

confidence: 99%

“…3, each band is very flat over the k-space, and the bands with similar energy levels seem to form bundles. These very flat bands indicate strongly localized electron distribution in the lattice, and the bundle-like structure is reflected in the highly degenerated molecular orbitals of the [Mo 6 Cl 14 ] 2¹ complex. The calculated band gap energies (E g ) are listed in Table 3.…”

Section: Computational Analysesmentioning

confidence: 99%

“…16 Then, the sample was heated on a hot plate at 150°C for 1 h in a glove box filled with well-dried N 2 gas, where the concentration of water was less than 0.1 ppm. Because the lattice structure of Cs 2 [Mo 6 Cl 14 ] is highly sensitive to the presence of water molecules absorbed from ambient moisture, 26) this heat treatment needs to remove the water molecules from the lattice so that the intrinsic nature of the compound can be evaluated.…”

Section: Introductionmentioning

confidence: 99%

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Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs2[Mo6Cl14] using various DFT functionals

Saito

Lemoine

Cordier

et al. 2017

J. Ceram. Soc. Japan

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The electronic and structural characteristics of the octahedral molybdenum cluster-based ternary compound, Cs 2 [Mo 6 Cl 14 ], were investigated based on density functional theory (DFT) and subsequent comparisons with experimentally observed results. The geometry optimization and band structure calculations of Cs 2 [Mo 6 Cl 14 ] were performed using three standard functionals: local density approximation, Perdew-Burke-Ernzerhof (PBE) as a generalized gradient approximation, and PBE revised for solid compounds (PBEsol). The validity of the calculated results was experimentally examined via X-ray powder diffraction, ultraviolet visible (UVvis) diffuse reflection, and X-ray photoemission spectra (XPS) measurements. PBEsol was found to show the best performance in terms of reproducing the experimentally refined lattice structure of the compound. The calculated band gap energy (E g ) was consistent with the value evaluated from the UVvis measurement. Furthermore, the XPS valence spectrum of the compound was well reproduced by the calculated projected density of state weighted with the photoionization probabilities of Al K ¡ . Although the spectral shapes simulated using the three functionals were similar, PBEsol reproduced the energy levels of the electronic states of both [Mo 6 Cl 14 ] 2¹ and Cs + ion with greater consistency. Therefore, it was concluded that PBEsol is the most appropriate functional for DFT calculations of the metal cluster-based lattice system.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Computational Analysesmentioning

confidence: 99%

Section: Computational Analysesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs2[Mo6Cl14] using various DFT functionals

Saito

Lemoine

Cordier

et al. 2017

J. Ceram. Soc. Japan

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Molecular and Supramolecular Arrays of the [ Re ₆ (μ ₃ ‐ Se ) ₈ ] ²⁺ Core‐Containing Clusters

Zheng

2005

Encyclopedia of Inorganic Chemistry

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Transition metal clusters are a unique class of chemical substances. Not only do they have well‐defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal–metal bonded species. In this contribution, our efforts in developing synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability are summarized. Specifically, we have explored the uses of site‐differentiated cluster complexes of the [Re 6 (μ 3 ‐Se) 8 ] 2+ core as stereospecific building blocks for supramolecular construction. A great variety of cluster‐supported molecular and supramolecular architectures have been realized. These include Tinkertoy‐like molecular cluster arrays featuring cluster units bridged by multitopic ligands and supramolecular assemblies of clusters engineered via hydrogen bonding and metal–ligand coordination. Some of these nanoscopic cluster‐containing systems display rather interesting electronic and spectroscopic properties and, therefore, hold great potential in developing molecule‐based electronic and optical materials. The work therefore marks the beginning of what promises to be an exciting new chapter in cluster chemistry.

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Cluster‐Based Supramolecular Compounds from Mo(W)/Cu/S Cluster Precursors

Liu

Zhang

et al. 2009

Design and Construction of Coordination Polymers

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Extended materials based on the [Mo6Cl8]4+ building block bridged by 4,4′-bipyridine

Cited by 34 publications

References 26 publications

Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs<sub>2</sub>[Mo<sub>6</sub>Cl<sub>14</sub>] using various DFT functionals

Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs<sub>2</sub>[Mo<sub>6</sub>Cl<sub>14</sub>] using various DFT functionals

Molecular and Supramolecular Arrays of the [ Re ₆ (μ ₃ ‐ Se ) ₈ ] ²⁺ Core‐Containing Clusters

Cluster‐Based Supramolecular Compounds from Mo(W)/Cu/S Cluster Precursors

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Extended materials based on the [Mo6Cl8]4+ building block bridged by 4,4′-bipyridine

Cited by 34 publications

References 26 publications

Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs<sub>2</sub>[Mo<sub>6</sub>Cl<sub>14</sub>] using various DFT functionals

Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs<sub>2</sub>[Mo<sub>6</sub>Cl<sub>14</sub>] using various DFT functionals

Molecular and Supramolecular Arrays of the [ Re 6 (μ 3 ‐ Se ) 8 ] 2+ Core‐Containing Clusters

Cluster‐Based Supramolecular Compounds from Mo(W)/Cu/S Cluster Precursors

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Molecular and Supramolecular Arrays of the [ Re ₆ (μ ₃ ‐ Se ) ₈ ] ²⁺ Core‐Containing Clusters