Structure, optical and electro-physical properties of tetramerized anion-radical salt (N-Xy-Qn)(TCNQ)2.

The (N-Xy-Qn)(TCNQ)2 anion-radical salt characterized by tetramerized stacks of the TCNQ acceptor molecules has been synthesized and characterized using vibrational spectroscopy and electrical resistivity measurements. The bond lengths analysis based on the crystal structure data, indicates that the TCNQ molecules are non-uniformly charged with -0.83 e localized on the inner B molecules and -0.33 e on the outer A molecules within ABBA tetramers. Both infrared and Raman spectra of (N-Xy-Qn)(TCNQ)2 are dominated by vibrational modes of TCNQ and display splitting related to the tetramerized structure. Many of these features are affected by the strong electron-molecular vibration (EMV) coupling. Other charge-sensitive modes allowed estimation of charge localized on TCNQ, with the results that confirm the charges estimated on basis of the crystal data. Electrical measurements revealed the low-conducting behavior with room temperature conductivity value of 2.6 mS cm-1 and temperature dependence of resistivity that can be explained within the band conduction model. The calculated activation energies range from 0.169 eV to 0.187 eV, depending on the crystallographic direction and thermal history of the sample.

Charge localization in 1D tetramerized organic conductors: the special case of (tTTF)2ClO4.

We report a detailed structural and spectroscopic study of the 1D 2:1 cation radical salt (tTTF)2ClO4, where tTTF = trimethylenetetrathiafulvalene, which exhibits a semiconductor-semiconductor phase transition at ca. T = 137 K. Crystal structures are determined above and below the transition; the tTTF molecules in stacks are grouped into weakly interacting tetramers. The reorganization of tTTF stacks is accompanied with an order-disorder transition in anion sublattice. Polarized infrared and Raman spectra of (tTTF)2ClO4 are measured in the broad frequency range as a function of the temperature (10-293 K). The structural and vibrational features are investigated to elucidate the origin of the semiconductor-semiconductor phase transition. We discuss the electron-intramolecular vibration coupling effects in the vibrational spectra of (tTTF)2ClO4 and identify signatures of high- and low-temperature states of charge localization in the tetramerized system. Both the C=C and C-S stretching modes of tTTF give evidence of strong charge distribution fluctuations in conducting stacks for T > 137 K, which are responsible for the appearance of molecules with charge +1e, and charge localization in tTTF tetramers for T < 137 K. The uniqueness of the salt (tTTF)2ClO4 in comparison with other tetramerized 1D systems is discussed.

The metal-insulator transition in the organic conductor ß″-(BEDT-TTF)2Hg(SCN)2Cl.

We explore the nature of the metal-insulator transition in the two-dimensional organic compound ß″-(BEDT-TTF)2Hg(SCN)2Cl by x-ray, electrical transport, ESR, Raman, and infrared investigations. Magnetic and vibrational spectroscopy concurrently reveal a gradual dimerization along the stacking direction (a-b), setting in already at the crossover temperature of 150 K from the metallic to the insulating state. A spin gap of Δσ=47 meV is extracted. From the activated resistivity behavior below T = 55 K, a charge gap of Δρ=60 meV is derived. At TCO = 72 K, the C=C vibrational modes reveal the development of a charge-ordered state with a charge disproportionation of 2δρ=0.34e. In addition to a slight structural dimerization, charge-order causes stripes most likely perpendicular to the stacks.

Generation of Low-Dimensional Architectures through the Self-Assembly of Pyromellitic Diimide Derivatives.

Small π-conjugated molecules can be designed and synthesized to undergo controlled self-assembly forming low-dimensional architectures, with programmed order at the supramolecular level. Such order is of paramount importance because it defines the property of the obtained material. Here, we have focused our attention to four pyromellitic diimide derivatives exposing different types of side chains. The joint effect of different noncovalent interactions including π-π stacking, H-bonding, and van der Waals forces on the four derivatives yielded different self-assembled architectures. Atomic force microscopy studies, corroborated with infrared and nuclear magnetic resonance spectroscopic measurements, provided complementary multiscale insight into these assemblies.

Inter-layer charge disproportionation in the dual-layer organic metal (tTTF-I)2ClO4 with unsymmetrical I···O halogen bond interactions.

A mixed-valence salt of tTTF-I with ClO4(-), formulated as (tTTF-I)2ClO4, is characterized by the presence of two crystallographically independent donor molecules, segregated in different layers and linked together through I···O interactions with the ClO4(-) anion disordered at room temperature. The tTTF-I donor molecule was prepared by metallation of tTTF (trimethylene tetrathiafulvalene) followed by reaction with iodine to afford the mono and diiodo derivatives tTTF-I and tTTFI2, respectively. The crystal structure of the latter neutral tTTFI2 shows the occurrence of strong type II, II halogen bond interactions. Band structure calculations of the dual-layer structure of the 2 : 1 salt (tTTF-I)2ClO4 show co-existence of both 1D open and 2D closed Fermi surfaces. The salt undergoes a metal-insulator phase transition at T(MI) = 90 K, associated with an electronic dimensionality decrease, since already at 100 K, the 2D part of the Fermi surface transforms into 1D corrugated planes. High resolution X-ray investigations performed at 100 K, combined with multipolar refinements, indicate an approximately equivalent +0.5e charge in both donor molecules, as also deduced from the intramolecular bond distances. On the other hand, Raman spectroscopic investigations show that at ambient temperature the charge is actually distributed non-uniformly in conducting layers of tTTF-I molecules, with the identification of molecules with charges +1, +0.5, 0e, while at low temperature the charge distribution becomes essentially uniform (+0.5e), as confirmed from the X-ray high resolution data. These apparently contradictory behaviors are actually a consequence of a partial electron transfer between the two independent slabs to reach a common Fermi level in the metallic phase.

Charge fluctuations and ethylene-group-ordering transition in ß''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋠Y molecular charge-transfer salts.

The polarized infrared reflectance and Raman spectra of the three quasi-two-dimensional ß''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅Y bifunctional charge-transfer salts, where BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene and Y = C6H5Br, (C6H5CN)0.17(C6H5Br)0.83, (C6H5CN)0.4(C6H5F)0.6, have been measured as a function of the temperature. Signatures of charge inhomogenity have been found in both Raman and infrared spectra of the ß''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅Y superconductors. A 100 K transition to a mixed insulating/metallic state is clearly seen for the first time in the temperature dependence of the electronic spectra of superconducting ß''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅C6H5Br. We suggest that this phase transition is due to subtle changes in the ethylene groups ordering, which are related to a structural phase transition in the anionic layer. The infrared and Raman spectra of quasi-two-dimensional metal α-'pseudo-κ'-(BEDT-TTF)4[(H3O)Fe(C2O4)3]C6H4Br2 are also investigated.

Spectroscopic studies of the phase transition from the mott insulator state to the charge-ordering state of κ-(ET)4[M(CN)6][N(C2H5)4]·2H2O (M = Co(III) and Fe(III)) salts.

Polarized reflectivity spectra versus temperature of two isostructural charge-transfer salts κ-(ET)4[M(CN)6][N(C2H5)4]·2H2O (M = Co(III) and Fe(III)) (ET = bis(ethylenedithio)tetrathiafulvalene) were studied. The electronic and vibrational spectra exhibit a drastic change at around 150 K. On the basis of the spectral analysis, we deduced the nature of the phase transition. The phase transition at 150 K is due to a charge ordering; above this temperature, strong charge fluctuations are observed.

Charge-assisted halogen bonding: donor-acceptor complexes with variable ionicity.

Charge-assisted halogen bonding is unambiguously revealed from structural and electronic investigations of a series of isostructural charge-transfer complexes derived from iodinated tetrathiafulvalene and tetracyanoquinodimethane derivatives, (EDT-TTFI2)2(TCNQF(n)), n=0-2, which exhibit variable degrees of ionicity. The iodinated tetrathiafulvalene derivative, EDT-TTFI2, associates with tetracyanoquinodimethane (TCNQ) and its derivatives of increasing reduction potential (TCNQF, TCNQF2) through highly directional C-I⋅⋅⋅N≡C halogen-bond interactions. With the less oxidizing TCNQ acceptor, a neutral and insulating charge-transfer complex is isolated whereas with the more oxidizing TCNQF2 acceptor, an ionic, highly conducting charge-transfer salt is found, both of 2:1 stoichiometry and isostructural with the intermediate TCNQF complex, in which a neutral-ionic conversion takes place upon cooling. A correlation between the degree of charge transfer and the C-I⋅⋅⋅N≡C halogen-bond strength is established from the comparison of the structures of the three isostructural complexes at temperatures from 300 to 20 K, thus demonstrating the importance of electrostatics in the halogen-bonding interaction. The neutral-ionic conversion in (EDT-TTFI2)2(TCNQF) is further investigated through the temperature dependence of its magnetic susceptibility and the stretching modes of the C≡N groups.

Experimental and theoretical investigation of vibrational spectra of coordination polymers based on TCE-TTF.

The room-temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7-tetrakis(2-cyanoethylthio)-tetrathiafulvalene (TCE-TTF) with paramagnetic (Co(II), Mn(II)) and diamagnetic (Zn(II), Cd(II)) ions, together with BF(4)(-) or ClO(4)(-) anions are reported. Infrared and Raman-active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE-TTF using density functional theory (DFT) methods. It is confirmed that the TCE-TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C=C stretching vibrations of TCE-TTF are analyzed assuming the occurrence of electron-molecular vibration coupling (EMV). The presence of the antisymmetric C=C dimeric mode provides evidence that charge transfer takes place between TCE-TTF molecules belonging to neighboring polymeric networks.

Structural distortions upon oxidation in heteroleptic [Cp(2)W(dmit)] tungsten dithiolene complex: combined structural, spectroscopic, and magnetic studies.

Four different cation radical salts are obtained upon electrocrystallization of [Cp(2)W(dmit)] (dmit = 1,3-dithiole-2-thione-4,5-dithiolato) in the presence of the BF(4)(-), PF(6)(-), Br(-), and [Au(CN)(2)](-) anions. In these formally d(1) cations, the WS(2)C(2) metallacycle is folded along the S···S hinge to different extents in the four salts, an illustration of the noninnocent character of the dithiolate ligand. Structural characteristics and the charge distribution on atoms, for neutral and ionized complexes with various folding angles, were calculated using DFT methods, together with the normal vibrational modes and theoretical Raman spectra. Raman spectra of neutral complex [Cp(2)W(dmit)] and its salts formed with BF(4)(-), AsF(6)(-), PF(6)(-), Br(-), and [Au(CN)(2)](-) anions were measured using the red excitation (λ = 632.8 nm). A correlation between the folding angle of the metallacycle and the Raman spectroscopic properties is analyzed. The bands attributed to the C═C and C-S stretching modes shift toward higher and lower frequencies by about 0.3-0.4 cm(-1) deg(-1), respectively. The solid state structural and magnetic properties of the three salts are analyzed and compared with those of the corresponding molybdenum complexes. Temperature dependence of the magnetic susceptibility shows the presence of one-dimensional antiferromagnetic interactions in the BF(4)(-), PF(6)(-), and [Au(CN)(2)](-) salts, while an antiferromagnetic ground state is identified in the Br(-) salt below T(Néel) = 7 K. Interactions are systematically weaker in the tungsten salts than in the isostructural molybdenum analogs, a consequence of the decreased spin density on the dithiolene ligand in the tungsten complexes.

New tetrathiapentalene-derived charge transfer salts with paramagnetic transition metal complex anion: kappa-(EDDH-TTP)(3)[Cr(phen)(NCS)(4)] x 2CH(2)Cl(2) and kappa(21)-(BDH-TTP)(5)[Cr(phen)(NCS)(4)](2) x 2CH(2)Cl(2).

The preparation, crystal structures, and optical and magnetic properties of two new charge-transfer salts kappa-(EDDH-TTP)(3)[Cr(phen)(NCS)(4)] x 2CH(2)Cl(2) (1) and kappa(21)-(BDH-TTP)(5)[Cr(phen)(NCS)(4)](2) x 2CH(2)Cl(2) (2), where phen = 1,10- phenanthroline, EDDH-TTP = 2-(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-5-(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, and BDH-TTP = 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, are reported. Crystal data: (1) monoclinic P2(1)/a, a = 25.0752(5) A, b = 10.6732(3) A, c = 28.1601(6) A, beta = 95.195(2) degrees, Z = 4, R = 0.0585 for 6741 independent reflections with I > 3 sigma(I); (2) monoclinic P2(1)/a, a = 23.8275(4) A, b = 9.1015 (2) A, c = 27.0420(1) A, beta = 99.9297(8) degrees, Z = 4, R = 0.0530 for 4565 independent reflections with I > 2 sigma(I). The crystal structures for both compounds consist of alternating organic and inorganic layers. The organic layer in compound 1 is characterized as kappa-type, while the organic layer in 2 resembles the kappa-type but it contains orthogonal dimers and monomers, and it is therefore called kappa(21). Compound 1 shows metallic behavior down to low temperature. Salt 2 shows semiconductive behavior, which is explained as the result of either charge ordering owing to the kappa(21)-type structure or Peierls distortion due to the one-dimensional electronic nature. However, weak metallic behavior could be observed at 10 kbar above ca. 150 K and at 15 kbar above 170 K. The magnetic susceptibilities for both compounds show Curie-Weiss behavior, showing that the exchange interactions between the magnetic anions are weak. Polarized reflectance spectra of single crystals were measured over the spectral range from 650 to 7000 cm(-1). Moreover, absorption and diffusion reflectance spectra of powdered crystals dispersed in KBr (from 400 to 7000 cm(-1)) were recorded. Vibrational and electronic features are discussed.