A novel type of two-dimensional pattern of association of mixed-valence dimers in the structures of two cation radical salts of thieno- and selenolo[3,4-d]-1,3-dithiol-2-ylidene and a monovalent hexanuclear chalcohalide rhenium cluster anion

Gabriel, Jean‐Christophe P.; Johannsen, I.; Batail, Patrick; Coulon, C.

doi:10.1107/s0108270193001076

Cited by 6 publications

(4 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In both complexes, the bond lengths in the thiophenic ring are close to those found in the corresponding TTF‐based donors 16b, 18. The Au−S bond lengths observed in these complexes, with an average value of 2.319 Å (see Table 1), are in the upper range of values reported for other gold( III ) dithiolates15d, 19 that extend from 2.29 to 2.34 Å with an average of 2.305 Å.…”

Section: Resultssupporting

confidence: 64%

Gold Complexes with Dithiothiophene Ligands: A Metal Based on a Neutral Molecule

Belo¹,

Alves²,

Lopes³

et al. 2001

Chem. Eur. J.

114

View full text Add to dashboard Cite

The gold complexes n-Bu4N[Au(alpha-tpdt)2] (5), n-Bu4N[Au(dtpdt)2] (4) and n-Bu4N[Au(tpdt)2] (6) based on new dithiothiophene ligands (alpha-tpdt= 2,3-thiophenedithiolate, dtpdt=2,3-dihydro-5,6-thiophenedithiolate and tpdt = 3,4-thiophenedithiolate) have been prepared and characterised. These gold(III) complexes are diamagnetic, but they can be oxidised with iodine to the paramagnetic compounds [Au(alpha-tpdt)2] (8), [Au(dtpdt)2] (7) and n-Bu4N[[Au(tpdt)2]n-2] (9), which were isolated as fine powders and which exhibit paramagnetic susceptibilities that are almost temperature independent with room temperature values of 2.5 x 10(-4), 2.0 x 10(-4) and 5 x 10(-4) emu x mol(-1), respectively. Interestingly, the neutral complex [Au(alpha-tpdt)2] (8) as a polycrystalline sample displays the properties of a metallic system with a room temperature electrical conductivity of 6 S x cm(-1) and a thermoelectric power of 5.5 microVK(-1); this is the first time that this metallic property has been observed in a molecular system based on a neutral species.

show abstract

Section: Resultssupporting

confidence: 64%

Gold Complexes with Dithiothiophene Ligands: A Metal Based on a Neutral Molecule

Belo¹,

Alves²,

Lopes³

et al. 2001

Chem. Eur. J.

114

View full text Add to dashboard Cite

show abstract

“…Both the peak-to-peak linewidth (DH pp ) and the g factor values exhibit a sinusoidal dependence on the angle of the applied magnetic field, the extreme values of the g factor being 2.0021, 2.0052 and 2.0131, which are almost identical to those found in the salt [(DT-TTF) 2 Re 6 S 5 Cl 9 ´2 C 3 H 7 NO], where strongly coupled, singly oxidised [(DT-TTF) 2 ] . dimers exist, [36] and agree with the molecular orientations of the radical cations in the crystal. Thus, the minimum g value observed for this salt is close to the free-electron value of 2.0023, as expected for any planar sulfur p-donor radical cation with the axis perpendicular to the molecular plane oriented parallel to the applied magnetic field (H 0 ), where the contribution of the spin ± orbit coupling is very small.…”

Section: Magnetic Propertiessupporting

confidence: 64%

The [(DT-TTF)2M(mnt)2] Family of Radical Ion Salts: From a Spin Ladder to Delocalised Conduction Electrons That Interact with Localised Magnetic Moments

Ribera¹,

Rovira²,

Veciana³

et al. 1999

Chem. Eur. J.

View full text Add to dashboard Cite

Electrocrystallisation of the p-electron donor dithiopheno-tetrathiafulvalene (DT-TTF) with maleonitrile dithiolate (mnt) ± metal (M) complexes gives rise to the new family of radical ion salts [(DT-TTF) 2 M(mnt) 2 ] (M Au, Pt, Ni), which are isostructural and crystallise in the monoclinic space group P2 1 /n forming regular segregated stacks of donor and acceptor molecules along the b axis. The DT-TTF stacks are paired and interact strongly through S´´´S contacts in a ladder-like motif. The three salts have quite high room-temperature electrical conductivities (9, 40 and 40 S cm À1 for M Au, Pt and Ni respectively) but their conductivity ± temperature dependencies differ. The Au salt has an activated conductivity at room temperature whereas the Ni and Pt salts are metal-like at room temperature and both exhibit a metal ± insulator transition around 120 K. These contrasting transport properties are accounted for by the differences in the transfer integrals along the DT-TTF stacks. The magnetic susceptibility of the salt with M Au, in which the [Au(mnt) 2 À ] anion is diamagnetic, can be fitted to a twolegged spin-ladder model. From diffuse X-ray scattering studies it is established that below 220 K the donors dimerise along the b stacking direction, and the spin carrier units in the ladder are identified as those formed by dimerised donors [(DT-TTF) 2 ]. . Observation in their EPR spectra of a single line which increases dramatically in width as the conductivity increases is evidence for the presence of two magnetic subsystems which interact in the salts (M Ni, Pt) with paramagnetic [M(mnt) 2 ] À ions.

show abstract

“…Furthermore, the development of a solution chemistry of large, isostructural and isosteric chalcohalide metal cluster anions such as Re 6 Q 5 Cl 9 - , − Re 6 Q 6 Cl 8 2- , , (Q = S, Se), has offered unique opportunities for the construction of novel families of cation radical salts based on TTF, TMTTF, DTTTF, or BEDT-TTF. Of particular interest is the series of two-dimensional phases formulated as β-(BEDT-TTF) 4 [Re 6 Q 6 Cl 8 ]·(solvent), (Q = S, Se; solvent = DMF, THF, dioxane, H 2 O), whose macroscopic metallic properties may be fine-tuned from the neutral molecular (solvent) guest site upon significant manipulation of the collective response of a precise set of C−H π - donor ···O guest hydrogen bonds. , Polyoxometalate anions also offer a large number of counteranions of various shapes and magnetic states for the elaboration of molecular materials by electrocrystallization, as recently reviewed by Coronado and Gómez-García .…”

Section: Electrocrystallization: a Wide Variety Of Partnersmentioning

confidence: 99%

Electrocrystallization, an Invaluable Tool for the Construction of Ordered, Electroactive Molecular Solids

et al. 1998

View full text Add to dashboard Cite

For the past three decades, the electrocrystallization technique has been used extensively to assemble a large variety of molecular ions into long range ordered single crystals of high purity. This effort is reviewed in the present paper from the initial vigorous impetus triggered by the development of organic (molecular) metals and superconductors to the continuous diverse developments toward insulating antiferromagnetic systems, the synthesis of crystals of coordination polymers, the construction of ternary and quaternary phases, the variation of molecular conformation, the use of polyfunctionalized π-donor molecules with hydrogen-bond-donor and/or -acceptor capabilities and the development of molecular alloys, with the aim of exemplifying an approach to the solid-state chemistry of molecular ions.

show abstract

A novel type of two-dimensional pattern of association of mixed-valence dimers in the structures of two cation radical salts of thieno- and selenolo[3,4-d]-1,3-dithiol-2-ylidene and a monovalent hexanuclear chalcohalide rhenium cluster anion

Abstract: nonachloropentathiahexarhenate-dimethylformamide (1/2), (2CloH4SaSe2)+.Re6SsC19

Cited by 6 publications

References 5 publications

Gold Complexes with Dithiothiophene Ligands: A Metal Based on a Neutral Molecule

Gold Complexes with Dithiothiophene Ligands: A Metal Based on a Neutral Molecule

The [(DT-TTF)2M(mnt)2] Family of Radical Ion Salts: From a Spin Ladder to Delocalised Conduction Electrons That Interact with Localised Magnetic Moments

Electrocrystallization, an Invaluable Tool for the Construction of Ordered, Electroactive Molecular Solids

Contact Info

Product

Resources

About