Density functional investigation of the molecular structures, vibrational and absorption spectra of metal thiolate complexes, M(SC6H5)3 (M=As, Sb or Bi)

He, Yonghui; Bin, Yannan; Liang, Yi‐Zeng; Xiang, Juan

doi:10.1016/j.comptc.2012.06.023

Cited by 9 publications

(2 citation statements)

References 32 publications

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“…In general, s 2 -metal cations can feature MC (metal-centred) sp transitions andif ligands with low-lying HOMOs are bondedalso LMCTs. [45][46][47] An MC sp transition results in a considerable geometrical distortion of the molecule in the excited state, which leads either to an efficient quenching and non-emissive behaviour or to a large Stokes shift of the emission, as observed for 7 (Fig. 7).…”

Section: Photophysical Characterizationmentioning

confidence: 77%

The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(iii) ions

et al. 2013

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Alkali metal salts of a novel Janus scorpionate ligand [(Tr(Me))](-) with hard and soft donor sites (N, S) were synthesized by the reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with NaBH4 and KBH4, respectively, via Trofimenko's protocol. The resulting compounds were the sodium and potassium complexes [Na(Tr(Me))] (1), [K(Tr(Me))] (2) and the mixed ion compound [KNa(Tr(Me))] (3). [K(Tr(Me))] (2) was reacted with bismuth(III) chloride to afford the complexes [Bi(Tr(Me))(Cl)(μ-Cl)2]2 (5) and [Bi(Tr(Me))(Cl)2(μ-Cl)]n (6). Compound 5 was formed when 2 was applied to BiCl3 in a molar ratio 2:1, while 6 was achieved when a ratio of 1:1 was used. The reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with BiCl3 led to the formation of the complex [Bi(L)4(Cl)2]Cl (7). The products were characterized by NMR and IR spectroscopy, elemental analyses and mass spectrometry. Solid state structures were determined by X-ray diffraction of single crystals of 1, 3, 3a, 5, 6 and 7. The alkali metal scorpionates 1-3 are coordination polymers with alternating orientation of the ligands. They dissociate in solution as observed in NMR measurements. Negative mode ESI-MS data also indicate the presence of monomers. The bismuth complex 5 is dimeric and 6 is polymeric, and both are bridged via chloro ligands. The three bismuth complexes 5, 6 and 7 have highly distorted octahedral coordination geometries. The influence of the stereochemically active lone pair was found to be most pronounced in the dimeric complex 5. The ligand Tr(Me) and all bismuth complexes were also screened for their photo-luminescence activity. Whereas solutions of Tr(Me) exhibit no luminescence, 7 is only emissive at 77 K, and 5 is emissive both at r.t. and 77 K.

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Section: Photophysical Characterizationmentioning

confidence: 77%

The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(iii) ions

et al. 2013

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“…In cases where electron rich ligands are bonded, also ligand to metal charge transfer states (LMCTs) are possible. [42][43][44][45] Therefore, this long wavelength absorption of 4 might be due to s-p transitions and/or a S→Bi LMCT with the highest occupied molecular orbital (HOMO) located on the electron-rich sulphur atom. Interestingly, no comparable low energy bands could be detected for 5.…”

Section: Photophysical Characterisationmentioning

confidence: 99%

Borate-based ligands with two soft heterocycle/thione groups and their sodium and bismuth complexes

et al. 2014

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Two novel sodium complexes [NaBb] (1) (Bb = dihydrobis(2-mercapto-benzimidazolyl)borate) and [NaBt(Me)] (2) (Bt(Me) = dihydrobis(2-mercapto-4-methylthiazolyl)borate) have been prepared and characterized by using two heterocycles, 2-mercapto-benzimidazole and 2-mercapto-4-methylthiazole, as well as NaBH4 as precursors. The dipodal boron centred soft ligands Bb and Bt(Me) were prepared in situ. The reactivity of [NaBb] (1) and [NaBt(Me)] (2) towards Bi(III) ions has been studied. The resulting complex [BiBb2Cl] (3) contains an MS4 core with κ(3)-S,S,H coordination mode, while the complex [BiBt(Me)3] (4) with an MS6 core adopts a coordination mode κ(2)-S,S. A reaction of BiCl3 with the heterocyclic precursors 2-mercapto-benzimidazole (L(1)) and 2-mercapto-4-methylthiazole (L(2)) was also attempted; this afforded the monomeric [BiL(1)4Cl2][BiL(1)2Cl4] (5) and dimeric [BiL(2)2(μ-Cl)Cl]2 (6) bismuth complexes. The bismuth complexes possess distorted octahedral geometries except 3 for which a face-capped octahedron is found. The presence of (B)H···Bi interactions has been identified by X-ray diffraction in 3 with a H···Bi distance of 2.58(1) Å which is uniquely short and unprecedented. Two of the synthesized complexes (4 and 5) have been investigated by luminescence spectroscopy. They feature emission bands in the solid state at room temperature at 674 (4) and 586 nm (5), which are hypsochromically shifted in (frozen) ethanolic solutions at 77 K to 618 and 537 nm, respectively.

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Surface Functionalization of Surfactant‐Free Particles: A Strategy to Tailor the Properties of Nanocomposites for Enhanced Thermoelectric Performance

et al. 2022

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The broad implementation of thermoelectricity requires high-performance and low-cost materials. One possibility is employing surfactant-free solution synthesis to produce nanopowders. We propose the strategy of functionalizing "naked" particles' surface by inorganic molecules to control the nanostructure and, consequently, thermoelectric performance. In particular, we use bismuth thiolates to functionalize surfactant-free SnTe particles' surfaces. Upon thermal processing, bismuth thiolates decomposition renders SnTe-Bi 2 S 3 nanocomposites with synergistic functions: 1) carrier concentration optimization by Bi doping; 2) Seebeck coefficient enhancement and bipolar effect suppression by energy filtering; and 3) lattice thermal conductivity reduction by small grain domains, grain boundaries and nanostructuration. Overall, the SnTe-Bi 2 S 3 nanocomposites exhibit peak z T up to 1.3 at 873 K and an average z T of � 0.6 at 300-873 K, which is among the highest reported for solution-processed SnTe.

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Density functional investigation of the molecular structures, vibrational and absorption spectra of metal thiolate complexes, M(SC6H5)3 (M=As, Sb or Bi)

Cited by 9 publications

References 32 publications

The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(iii) ions

The versatile behaviour of a novel Janus scorpionate ligand towards sodium, potassium and bismuth(iii) ions

Borate-based ligands with two soft heterocycle/thione groups and their sodium and bismuth complexes

Surface Functionalization of Surfactant‐Free Particles: A Strategy to Tailor the Properties of Nanocomposites for Enhanced Thermoelectric Performance

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