Electronic localization in an extreme 1-D conductor: the organic salt (TTDM-TTF) [Au(mnt) ]

This article reports the investigation of a new low-dimensional organic salt, (TTDM-TTF)₂ [Au(mnt)₂], by single crystal X-ray diffraction, static magnetic susceptibility, EPR, thermopower, electrical resistivity measurements under pressure up to 25 kbar and band structure calculations. The crystal structure consists in a dimerized head to tail stacking of TTDM-TTF molecules separated by layers of orthogonal Au(mnt)₂ anions. The absence of overlap between neighboring chains coming from this particular crystal structure leads to an extreme one-dimensionality (1-D) for which the carriers of the half-filled conduction band become strongly localized in a Mott-Hubbard insulating state. This material is the first 1-D conductor in which the Mott-Hubbard insulating character cannot be suppressed under pressure. Received 15 April 2002 / Received in final form 17 June 2002 Published online 17 September 2002     

Infrared vibrational spectra of -histidinium dihydrogen orthophosphate orthophosphoric acid (LHP)

The entire vibrational spectrum of a single crystal of -histidinium dihydrogen orthophosphate orthophosphoric acid (LHP) was studied by infrared (IR) spectroscopy from 10 up to 4000 cm⁻¹. The polarized infrared (IR) reflectivity spectra were measured between 7 and 250 K, in the frequency range 10–600 cm⁻¹. From the IR spectral analysis, the phonon modes were classified within their symmetry species, and their longitudinal (LO) and transversal (TO) optical frequencies were calculated. A tentative assignment of the various internal modes observed in the transmissivity spectrum of LHP, between 300 and 4000 cm⁻¹, is proposed. The present study did not reveal any low-temperature structural phase transition.     

Separation of cross-relaxation and exchange in two-site spin systems without resolved couplings

Variable temperature two-dimensional nuclear Overhauser enhancement experiment (2-D NOESY) is used to extract the rate constants and cross-relaxation rates that contribute to the same cross-peaks in NOESY spectra. Rate constants (k _AB) and cross-relaxation rates (R _AB) for two-site spin systems are related to the ratio between the cross-peak and diagonal peak integrals (F) by the expression:R _AB -k _AB = (1/2τ _m)ln[(1 -F)/(1 +F)], where τ_m is the mixing time. As a model, we investigated the exchange processes in a system of dimer calix[4]arenes of C_4v symmetrical configuration with guest inclusion (benzene or benzene-d₆), where the measurement of exchange processes is hindered by the presence of strong nuclear Overhauser enhancement between protons in adjacent aromatic rings in the cone conformation of the calix[4]arene.     

Free radicals as host molecules

Perchlorotriphenylmethyl radical (1) and some of its radical derivatives form inclusion compounds with cyclic molecules. Thermal stabilities and crystal studies of some clatrates of1 are presented and discussed.     

Novel CuIII bis-1,2-dichalcogenene complexes with tunable 3D framework through alkaline cation coordination: a structural and theoretical study

The deprotonated form of the ligands pyrazine-2,3-diselenol (pds) and pyrazine-2,3-dithiol (pdt) react with Cu(ClO(4))(2).6 H(2)O to form different Cu(III) complexes Na[Cu(III)(pds)(2)].2 H(2)O (1), Li[Cu(III)(pds)(2)].3 H(2)O (2), and Na[Cu(III)(pdt)(2)].2 H(2)O (4) depending on the countercation compound used as deprotonating agent (NaOH, LiOH). Two other Cu(III) complexes were obtained by replacement of the alkali metal cations with tetrabutylammonium (TBA(+)), namely, TBA[Cu(III)(pds)(2)] (3), and TBA[Cu(III)(pdt)(2)] (5). All complexes were characterized by (1)H and (13)C NMR and IR spectroscopy, electronic absorption, elemental analysis, cyclic voltammetry (CV), and X-ray crystallography. Electrical conductivity measurements on single crystals show that these salts exhibit insulating behavior. The crystal structure of these species revealed a lateral coordination capability of the N atoms of the pyrazine ring of both pds and pdt ligands towards the alkali metal ions, which leads to the build up of a net of coordinative bonds, hydrogen bonds, and contacts that result in the final 3D structure. Two parameters control the crystal engineering of the final 3D structures: the nature of the alkali metal countercation and the nature of the chalcogen atom (Se/S), which allow fine-tuning of complex 3D crystal lattice. Density functional calculations were performed on the [Cu(pds)(2)] and [Cu(pdt)(2)] systems to investigate the electronic structure of the complexes and understand their electronic and electrochemical behavior by studying the frontier molecular orbitals. This study also reveals whether the redox processes take place on the ligands or on the metal center, a question under continuous discussion in the literature.     

Correlation between crystal structure and mobility in organic field-effect transistors based on single crystals of tetrathiafulvalene derivatives

Recently, it was reported that crystals of the organic material dithiophene-tetrathiafulvalene (DT-TTF) have a high field-effect charge carrier mobility of 1.4 cm(2)/(V x s). These crystals were formed by a simple drop-casting method, making this material interesting to investigate for possible applications in low-cost electronics. Here, organic single-crystal field-effect transistors based on materials related to DT-TTF are presented and a clear correlation between the crystal structure and the electrical characteristics is observed. The observed relationship between the mobilities in the different crystal structures is strongly corroborated by calculations of both the molecular reorganization energies and the maximum intermolecular transfer integrals. The most suitable materials described here exhibit mobilities that are among the highest reported for organic field-effect transistors and that are the highest reported for solution-processed materials.