Preparation and chemistry of new unsymmetrically substituted tetrachalcogenofulvalenes bearing CN(CH2)2X and HO(CH2)2X groups (X = S or Se)

Binet, Laurent; Fabre, J.M.; Montginoul, Claude; Simonsen, Klaus B.; Becher, Jan

doi:10.1039/p19960000783

Cited by 96 publications

(63 citation statements)

References 15 publications

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“…Suitable single crystals for an X-ray analysis (vide infra) were grown by slow evaporation of the solvent from a CH 2 Cl 2 solution of the complex. Similarly, deprotection of 4,5-bis[(2-cyanoethyl)thio]-4Ј,5Ј-ethylenedithiotetrathiafulvalene [29,30] with two equivalents of (Me 4 N·OH) in THF afforded the highly air sensitive TTF dithiolate. This was quenched with PhSbCl 2 to give complex 2, which was analyzed by 1 H and 13 C NMR spectroscopy, mass spectrometry and elemental analysis.…”

Section: Synthesesmentioning

confidence: 98%

Electron‐Rich Organoantimony(III) Dithiolate Complexes

2004

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Electron‐rich dithiolene complexes of the antimony(III) PhSb moiety, formulated as [SbPh(dddt)] (1) (dddt: 5,6‐dihydro‐1,4‐ditthine‐2,3‐dithiolate) and [SbPh(EDT‐TTFS2)] (2) (EDT‐TTFS2: 4,5‐ethylenedithio‐tetrathiafulvalene‐4′,5′‐dithiolate), have been prepared by deprotection of the corresponding precursors and trapping of the intermediate dithiolates with PhSbCl2. Both complexes have been structurally characterized. The analysis of their single‐crystal X‐ray structures shows original supramolecular organizations governed by secondary Sb···S contacts, with distorted octahedral coordination geometries around the Sb center. Band‐structure calculations for complex 2 reveal only weak dispersion of the valence and conduction bands, with an energy gap of 1.68 eV. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Synthesesmentioning

confidence: 98%

Electron‐Rich Organoantimony(III) Dithiolate Complexes

2004

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“…As shown in Scheme 1, the 13 C-enriched tmdt ligands were synthesized from 13 CS 2 according to the literature 17,18 , and the 13 C-enriched Zn(tmdt) 2 was synthesized according to Scheme 2 similar to the normal Zn(tmdt) 2 reported previously 14 . The deprotection of …”

Section: Appendixmentioning

confidence: 99%

Spin-gapped Mott insulator with the dimeric arrangement of twisted molecules Zn(tmdt) 2

et al. 2017

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Abstract13 C nuclear magnetic resonance measurements were performed for a single-component molecular material Zn(tmdt) 2 , in which tmdt's form an arrangement similar to the so-called κ-type molecular packing in quasi-two-dimensional Mott insulators and superconductors. Detailed analysis of the powder spectra uncovered local spin susceptibility in the tmdt π orbitals. The obtained shift and relaxation rate revealed the singlet-triplet excitations of the π spins, indicating that Zn(tmdt) 2 is a spin-gapped Mott insulator with exceptionally large electron correlations compared to conventional molecular Mott systems. 1A new type of molecular conductors M(tmdt) 2 (M = Ni, Au, Pt, Cu, and Pd) are of current interest not only because it is the first molecular metal composed of a single molecular species 1 but also affords novel electronic states owing to the multi-orbital nature, which conventional charge-transfer salts do not possess. Furthermore, the systems of M(tmdt) 2 are expected to host highly correlated electrons compared with conventional molecular materials with dimeric molecular structures called 2 : 1 compounds, where a dimer playing as one lattice site accommodates one carrier and thus the on-site Coulomb repulsion U is reduced by the spatial extension of the dimer orbital. In case that one molecule accommodates one carrier as in some of the systems M(tmdt) 2 , the U is not reduced by the dimerization.The M(tmdt) 2 consists of a single molecular species in which a transition-metal ion, M, is coordinated by molecular ligands, tmdt, from both sides 2,3 . The pπ molecular orbitals extended over the tmdt ligand lie near the Fermi level, whereas the energy level of the dpσ molecular orbital located around M strongly depends on M. 4-7 For M = Cu, the dpσ orbital lies close to the pπ orbitals, leading to the formation of a dpσ-pπ multi-orbital system 5,7 ;indeed, NMR studies of Cu(tmdt) 2 found that the dpσ and pπ orbitals host antiferromagnetic and spin-gapped Mott subsystems, respectively 8,9 . For M = Ni, Pt and Zn, the dpσ orbitals lie away (upward in the former two and downward in the latter) from the two pπ orbitals located near the Fermi level 4,10 . In these systems, two pπ orbitals in M(tmdt) 2 accommodate two electrons, likely giving pπ-band semimetals; the ab-initio band structure calculation predicts small Fermi pockets 4,10,11 . As expected, Ni(tmdt) 2 and Pt(tmdt) 2 are metals 1,10,12 and appreciable electron correlation was revealed by 13 C nuclear magnetic resonance (NMR) studies 13 .It is to be noticed, however, that Zn(tmdt) 2 is an insulator 14 ; the typical resistivity data are shown in Fig. 1 Fig. 1(a). In the 2 solid, two tmdt ligands are arranged face-to-face and they form a checker-board pattern in two-dimensional layers (Figs. 1(b) and (c)). This type of molecular arrangement is similar to the "κ-type configuration", which is familiar in the 2 : 1 charge-transfer salts represented by κ-(ET) 2 X, including dimer-Mott insulators and over-10-K superconductors 15 . Most remarkably, Zn(tmdt)...

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“…Compound 3 was synthesized according to the reported method [12] and the four CH 2 CH 2 CN groups were easily removed in the presence of CsOH·H 2 O. Similarly, compound 4, which contains four tosylate (OTs) groups, was prepared by the reported procedures.…”

Section: Resultsmentioning

confidence: 99%

Inclusion of Tetrachloroquinone and Metal Ions in a Macrotricyclic Molecule with a Tetrathiafulvalene Moiety Prompts Intermolecular Electron Transfer

Guo

Yang

et al. 2012

Asian J Org Chem

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A triptycene‐based cylindrical macrotricyclic molecule 1, which contains one tetrathiafulvalene (TTF) unit and four glycol chains, is reported. Both absorption and ESR spectroscopic studies clearly indicate that intermolecular electron transfer occurs from TTF in 1 to tetrachloroquinone in the presence of certain metal ions (e.g. Sc3+, Pb2+, and Zn2+). Based on comparative studies with 3 and 5, the close intermolecular alignment between 1 and tetrachloroquinone is proposed to occur by the synergic coordination of metal ions with oxygen atoms of the glycol chains and tetrachloroquinone (as well as the sulfur atoms of TTF). The intermolecular electron transfer is facilitated by the positive shift of the reduction potentials of tetrachloroquinone through coordination with metal ions, and the close alignment of 1 and tetrachloroquinone, which is beneficial for stabilizing the electron‐transfer state.

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Preparation and chemistry of new unsymmetrically substituted tetrachalcogenofulvalenes bearing CN(CH2)2X and HO(CH2)2X groups (X = S or Se)

Cited by 96 publications

References 15 publications

Electron‐Rich Organoantimony(III) Dithiolate Complexes

Electron‐Rich Organoantimony(III) Dithiolate Complexes

Spin-gapped Mott insulator with the dimeric arrangement of twisted molecules Zn(tmdt) 2

Inclusion of Tetrachloroquinone and Metal Ions in a Macrotricyclic Molecule with a Tetrathiafulvalene Moiety Prompts Intermolecular Electron Transfer

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