Synthesis and properties of bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate(1-) salts, [Q][Bi(dmit)2]. Crystal structure of [AsPh4][Bi(dmit)2]·1/2DMSO: comparison of the solid state structures of [Q][Bi(dmit)2] and [Q][Sb(dmit)2]

Comerlato, Nadia M.; Costa, Luiz Antônio S.; Howie, R. Α.; Pereira, Robson Pacheco; Rocco, Ana Maria; Silvino, Alexandre Carneiro; Wardell, Jámes L.; Wardell, Solange M. S. V.

doi:10.1016/s0277-5387(00)00643-4

Cited by 22 publications

(10 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[34] has showed that the size and geometry of the incorporated counteranion affects the conductivity mechanism of PPy films. The [Bi(dmit) 2 ] − [35] and [Sn(dmit) 3 ] 2− [36] anions in tetra-alkylammonium salts have distorted octahedral geometries, the geometry of the former being due to inter-anion metal-sulphur interactions. The geometries of these dmit based counter anions may not favor the parallel alignment of PPy chains, obstructing the channels responsible for the interchain charge transport and reducing the overall conductivity.…”

Section: Conductivitymentioning

confidence: 99%

Preparation, structure and electrochemistry of a polypyrrole hybrid film with [Pd(dmit)2]2−, bis(1,3-dithiole-2-thione-4,5-dithiolate)palladate(II)

Cruz

Wardell

Simão

et al. 2007

Electrochimica Acta

View full text Add to dashboard Cite

Section: Conductivitymentioning

confidence: 99%

Preparation, structure and electrochemistry of a polypyrrole hybrid film with [Pd(dmit)2]2−, bis(1,3-dithiole-2-thione-4,5-dithiolate)palladate(II)

Cruz

Wardell

Simão

et al. 2007

Electrochimica Acta

View full text Add to dashboard Cite

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] For instance, D 2d symmetry is present in Cu(II) and Zn(II) complexes, D 2h symmetry in Ni(II) complexes and C 2 symmetry for complexes of the Group 15 elements, Sb and Bi, in their trivalent oxidation state.…”

Section: Introductionmentioning

confidence: 99%

“…All the crystal structures of these complexes are known, [6][7][8][9][10][11][12][13][14][15] including those of the tetraethylammonium salts, a family showing an increasing degree of inter-anion interactions from the Zn to Bi complex. Therefore we could assess M-S inter-anion interactions in the solid state, by carefully comparing the gas-phase calculation to the solid-state bulk spectra of these systems.…”

Section: Introductionmentioning

confidence: 99%

“…The situation is different in the case of the anions in [10][11][12] or Bi [13][14][15] ): here there are metalsulfur inter-anion interactions, that raise the coordination number of the metal to 6, and that including the lone pair on the metal, provide highly distorted pseudo pentagonal bipyramidal geometries for Sb and Bi. While the cation, Q + , in each of the series, influences the anion arrangements and also the very weak S---S inter-anion interactions, the basic geometries about each of the two metals remain unaffected.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

Ferreira¹,

Comerlato²,

Wardell³

et al. 2004

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

Este trabalho apresenta uma investigação teórico-experimental dos espectros infravermelho/ Raman de diversos metais representativos coordenados com 1,3-ditiol-2-tiona-4,5-ditiolato (dmit), a saber [NEt 4 . Os espectros IV/Raman de todos os sólidos e também o espectro IV em solução do composto [NEt 4 ] 2 [Zn(dmit) 2 ] foram registrados de 4000 a 100 cm -1 . Duas regiões foram claramente identificadas: abaixo de 380 cm -1 os modos apresentaram forte contribuição metal-ligante, e acima, os modos indicaram majoritária contribuição do ligante. Os espectros IV/Raman do NEt 4 Br também foram registrados. As bandas vibracionais foram atribuídas a partir da análise de compostos relacionados, de publicações prévias e comparadas com amplo conjunto de cálculos ab initio realizados com diversos ECPs (SBK, Sttutgart), conjunto de bases (com e sem funções d) e metodologias (RHF, DFT e MP2). As geometrias, freqüências e intensidades foram calculadas e comparadas com as freqüências experimentais visando atribuições seguras. Assim, uma excelente concordância foi obtida para diversas bandas experimentais.This work reports a theoretical-experimental investigation of the infrared/Raman vibrational spectra of several metal 1,3-dithole-2-thione-4,5-dithiolate (dmit) complexes; [NEt 4 2 ] were recorded from 4000 to 100 cm -1 . Two regions were clearly identified: below 380 cm -1 , the modes presented significant metal-ligand contributions, and above, the modes indicated major ligand contributions. IR/Raman spectra of NEt 4 Br have also been recorded. The vibrational bands have been assigned starting from the analysis of related compounds, of previous published spectra and compared to several ECPs (SBK, Stuttgart), basis sets (with and without functions d) and methodologies (RHF, MP2 and DFT). Geometries, frequencies and intensities were calculated and compared to the experimental frequencies seeking secure assignment. Thus, an excellent agreement was obtained for several experimental bands.Keywords: IR, Raman, ab initio, RHF, DFT, MP2, dmit complexes, Zn, Sb, Bi IntroductionThe syntheses and properties of metal complexes with 1,2-dithiolato-polysulfido ligands have been intensely studied 1-3 particularly since the discovery, by Cassoux and co-workers 4 in 1986, of the first metallic molecular superconductor, [TTF][Ni(dmit) 2 ] 2 , where dmit is the 1,3-dithiole-2-thione-4,5-dithiolate ligand. Presently dmit ligand complexes are the best studied.The publication of Cassoux and co-workers 4 seminal paper led a new impetus for the study of the applications of metal dmit compounds as super-conducting complexes, materials with non-linear optical properties and materials for electronic molecular devices. Such properties arise in part, from the rich redox chemistry of these compounds and the large polarizability of sulfur atoms.An additional important feature for the super-conducting property on metal bis(dmit) complexes, such as [TTF][Ni(dmit) 2 ] 2 , is the planar geometry of the anions, [3][4][5] dmit 2- Despite the large volume of wo...

show abstract

“…The bis(dmit) anionic complexes of Zn(II) 47,48 and Cu(II) 49 present tetrahedral coordination spheres; quadratic plane for Ni(II), 4 and octahedral or bipyramidal for compounds with Sb(III) and Bi(III). 7 The crystalline packing for these systems is strongly influenced by the counterions and there are no interactions between the anion and the cation. However, in many complexes, there are very important interanionic π---π interactions and in the most of the cases they are responsible for the conduction properties in these materials.…”

Section: Resultsmentioning

confidence: 99%

Vibrational and Electronic Spectroscopy of Neutral Antimony Coordination Compounds of the 1,3-Dithiole-2-thione-4,5-dithiolate (dmit)

et al. 2012

View full text Add to dashboard Cite

The S 1s X-ray absorption near edge structure (XANES) and X-ray photoelectron spectra (XPS) of the neutral complexes [SbL(dmit)] (L = Br or I; dmit =1,3-dithiole-2-thione-4,5-dithiolate) have been measured using tunable synchrotron radiation. The valence shell electronic excitation by ultraviolet-visible (UV-vis) spectroscopy and the infrared vibrational spectra are presented and analyzed. The UV-vis results lead to an assignment of bands at 400 nm as π(Sm) → π*(C═S), where S(m) is the thiolate sulfur. The corresponding S 1s → π*(C═S) transition was identified at 2468.3 eV. Ab initio calculations, within the improved virtual orbital (IVO) method, carried out with the GSCF3 program, were applied to establish a complete and accurate spectral assignment. It has been the first attempt to apply such methodology for dmit coordination compounds, and very consistent results were obtained.

show abstract

Synthesis and properties of bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate(1-) salts, [Q][Bi(dmit)2]. Crystal structure of [AsPh4][Bi(dmit)2]·1/2DMSO: comparison of the solid state structures of [Q][Bi(dmit)2] and [Q][Sb(dmit)2]

Cited by 22 publications

References 18 publications

Preparation, structure and electrochemistry of a polypyrrole hybrid film with [Pd(dmit)2]2−, bis(1,3-dithiole-2-thione-4,5-dithiolate)palladate(II)

Preparation, structure and electrochemistry of a polypyrrole hybrid film with [Pd(dmit)2]2−, bis(1,3-dithiole-2-thione-4,5-dithiolate)palladate(II)

Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

Vibrational and Electronic Spectroscopy of Neutral Antimony Coordination Compounds of the 1,3-Dithiole-2-thione-4,5-dithiolate (dmit)

Contact Info

Product

Resources

About