Preparation of asymmetrical functionalized TTF; characterization of their charge transfer salts

Binet, Laurent; Montginoul, Claude; Fabre, Jean‐Marc; Ouahab, Lahcène; Golhen, Stéphane; Becher, Jan

doi:10.1016/s0379-6779(97)80922-8

Cited by 20 publications

(11 citation statements)

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“…Selectively 13 C-enriched Au(tmdt) 2 was synthesized in a way similar to that for normal Au(tmdt) 2 , which was reported previously [25]. The 13 C-enriched tmdt ligands were synthesized from 13 CS 2 according to the literature [30,31]. 13 C NMR measurements were performed for the fine polycrystals of 13 C-enriched Au(tmdt) 2 , where the outer parts of the double-bonded carbons in the center of tmdt were selectively enriched by 13 C isotopes as shown in Figs.…”

Section: Experimental Methodsmentioning

confidence: 99%

Multiorbital antiferromagnetic metal induced by intramolecular self-doping

Takagi

Gangi

Miyagawa

et al. 2020

Phys. Rev. Research

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The orbital of electrons in a solid affects their mutual interaction, which is a key to emergent phenomena. Therefore, control of the interplay between distinct orbitals makes the behavior of solids fertile. Such a case is substantiated by the aggregation of the molecule, M(tmdt) 2 , which contains π orbitals extended over the organic ligand, tmdt, and a level-tunable d orbital centered at the metal ion M. Among them, Au(tmdt) 2 exemplifies the critical π-d mixing, which arguably causes an over-100 K antiferromagnetic metal whose nature remains elusive. Here, we track the π-d interplay in Au(tmdt) 2 with dual orbital-resolved probes, 13 C NMR and synchrotron x-ray diffraction. We find substantial intramolecular (interorbital) redistribution of electrons on cooling, triggering a commensurate π-d antiferromagnetic metal to emerge, which invokes an orbital-selective doped Mott insulator caused by intramolecular self-doping. This demonstrates that vital traffic of electrons between distinct orbitals brings about an unique correlated phase.

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Section: Experimental Methodsmentioning

confidence: 99%

Multiorbital antiferromagnetic metal induced by intramolecular self-doping

Takagi

Gangi

Miyagawa

et al. 2020

Phys. Rev. Research

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Section: Appendixmentioning

confidence: 99%

“…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 the 13 C-enriched tmdt ligand using the MeOH solution of tetramethylammonium hydroxide in dry THF at room temperature yielded (Me 4 N + ) 2 ( 13 C-tmdt 2− ).…”

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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“…The bis-and mono-hydroxylated tetrathiafulvalenes 2a, 2b and 4a, 4b respectively, have been prepared as shown in Scheme 1 from the key cyano derivatives 1a and 1b 5,6 obtained via either a cross-coupling reaction (route a) and/or a Wittig-type reaction (route b) as already described in the literature. 6,7 The 4,5-bis(2-hydroxyethylthio)-4',5'-dimethyltetrathiafulvalene 2a{ 7 (also referred to as DHET-DMTTF) and the 4,5-bis(2-hydroxyethylthio)-4',5'-ethylenedithiotetrathiafulvalene 2b 6 (also referred to as DHET-EDTTTF), have been directly obtained in 71% and 82% yield respectively, by thiolate deprotection of the corresponding precursor 1a or 1b with sodium ethoxide in ethanol followed by treatment with 2chloroethanol 5±7 (vide infra). Similarly, the 4-(2-hydroxyethylthio)-5-methylthio-4',5'-dimethyltetrathiafulvalene 4a 8 (also referred to as HETMT-DMTTF) and the 4-(2-hydroxyethylthio)-5-methylthio-4',5'-ethylenedithiotetrathiafulvalene 4b 8 (also referred to as HETMT-EDTTTF), have been synthesized in 54 and 100% yield respectively, from the appropriate intermediate 3a or 3b by the thiolate deprotec-tion±alkylation procedure described below.…”

Section: Experimental Synthesismentioning

confidence: 99%

“…A series of radical cation salts derived from 2a±b and 4a±b have been prepared as reported in literature, 7,9 ). Unexpectedly, the (2a±AuBr 2 ) salt has ®nally been identi®ed (from X-ray structure determination) as the bromide salt.…”

Section: Electrochemistrymentioning

confidence: 99%

Synthesis and study of radical cation salts and TCNQ charge transfer complexes of a series of tetrathiafulvalenes (TTF) substituted by one or two hydroxylated side chain(s): –SCH2CH2OH

et al. 2000

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Unsymmetrically substituted tetrathiafulvalene derivatives containing hydroxy group(s) on side-chain(s) have been synthesized from cyano precursors via either a cross-coupling reaction or a Wittig-type condensation. As deduced from cyclic voltammetry data, the electron donor properties of the obtained compounds have been found to be similar to those of BEDTTTF. A series of radical cation salts derived from these donors has been obtained by electrocrystallization and charge transfer complexes have been prepared chemically by using TCNQ as an electron acceptor. The electrical conductivity of these phases ranges from 3610 22 to 7610 27 S cm 21 which is consistent with their structural features. X-Ray structural analysis of three of the radical cation salts with monovalent closed-shell anions (Br 2 , ClO 42 ) indicates a 1 : 1 stoichiometry which implies that, in each case, the donor has been oxidized to the D z state. In the same way, a crystal structure made of stacks where the donor and the acceptor molecules alternate has been found for a charge transfer complex between TCNQ and a donor derived from EDTTTF. The crystal structure of one of the donors indicates that the ¯exibility of the hydroxylated side chains appears as a favourable feature for the formation of hydrogen bonds.{Crystal data and structure determination details for 2a are available as supplementary data. For direct electronic access see http:// www.rsc.org/suppdata/jm/b0/b003009k/ {Compounds 2a, b and 4a, b have also been named as 2,3,6,7tetrasubstituted tetrathiafulvalenes.

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Preparation of asymmetrical functionalized TTF; characterization of their charge transfer salts

Cited by 20 publications

References 1 publication

Multiorbital antiferromagnetic metal induced by intramolecular self-doping

Multiorbital antiferromagnetic metal induced by intramolecular self-doping

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

Synthesis and study of radical cation salts and TCNQ charge transfer complexes of a series of tetrathiafulvalenes (TTF) substituted by one or two hydroxylated side chain(s): –SCH2CH2OH

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