Pressure-induced hydrogen localization coupled to a semiconductor-insulator transition in a hydrogen-bonded molecular conductor.

Purely organic crystals, κ-X3(Cat-EDT-TTF)2 [X = H or D, Cat-EDT-TTF = catechol-fused tetrathiafulvalene], are a new type of molecular conductor with hydrogen dynamics. In this work, hydrostatic pressure effects on these materials were investigated in terms of the electrical resistivity and crystal structure. The results indicate that the pressure induces and promotes hydrogen (deuterium) localization in the hydrogen bond, in contrast to the case of the conventional hydrogen-bonded materials (where pressure prevents hydrogen localization), and consequently leads to a significant change in the electrical conducting properties (i.e., the occurrence of a semiconductor-insulator transition). Therefore, we have successfully found a new type of pressure-induced phase transition where the cooperation of the hydrogen dynamics and π-electron interactions plays a crucial role.

Hydrogen-bond-dynamics-based switching of conductivity and magnetism: a phase transition caused by deuterium and electron transfer in a hydrogen-bonded purely organic conductor crystal.

A hydrogen bond (H-bond) is one of the most fundamental and important noncovalent interactions in chemistry, biology, physics, and all other molecular sciences. Especially, the dynamics of a proton or a hydrogen atom in the H-bond has attracted increasing attention, because it plays a crucial role in (bio)chemical reactions and some physical properties, such as dielectricity and proton conductivity. Here we report unprecedented H-bond-dynamics-based switching of electrical conductivity and magnetism in a H-bonded purely organic conductor crystal, κ-D3(Cat-EDT-TTF)2 (abbreviated as κ-D). This novel crystal κ-D, a deuterated analogue of κ-H3(Cat-EDT-TTF)2 (abbreviated as κ-H), is composed only of a H-bonded molecular unit, in which two crystallographically equivalent catechol-fused ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a +0.5 charge are linked by a symmetric anionic [O···D···O](-1)-type strong H-bond. Although the deuterated and parent hydrogen systems, κ-D and κ-H, are isostructural paramagnetic semiconductors with a dimer-Mott-type electronic structure at room temperature (space group: C2/c), only κ-D undergoes a phase transition at 185 K, to change to a nonmagnetic insulator with a charge-ordered electronic structure (space group: P1). The X-ray crystal structure analysis demonstrates that this dramatic switching of the electronic structure and physical properties originates from deuterium transfer or displacement within the H-bond accompanied by electron transfer between the Cat-EDT-TTF π-systems, proving that the H-bonded deuterium dynamics and the conducting TTF π-electron are cooperatively coupled. Furthermore, the reason why this unique phase transition occurs only in κ-D is qualitatively discussed in terms of the H/D isotope effect on the H-bond geometry and potential energy curve.

Gapless quantum spin liquid in an organic spin-1/2 triangular-lattice κ-H3(Cat-EDT-TTF)2.

We report the results of SQUID and torque magnetometry of an organic spin-1/2 triangular-lattice κ-H(3)(Cat-EDT-TTF)(2). Despite antiferromagnetic exchange coupling at 80-100 K, we observed no sign of antiferromagnetic order down to 50 mK owing to spin frustration on the triangular lattice. In addition, we found nearly temperature-independent susceptibility below 3 K associated with Pauli paramagnetism. These observations suggest the development of gapless quantum spin liquid as the ground state. On the basis of a comparative discussion, we point out that the gapless quantum spin liquid states in organic systems share a possible mechanism, namely the formation of a band with a Fermi surface possibly attributed to spinons.

Hydrogen bond-promoted metallic state in a purely organic single-component conductor under pressure.

Purely organic materials are generally insulating. Some charge-carrier generation, however, can provide them with electrical conductivity. In multi-component organic systems, carrier generation by intermolecular charge transfer has given many molecular metals. By contrast, in purely organic single-component systems, metallic states have rarely been realized although some neutral-radical semiconductors have been reported. Here we uncover a new type of purely organic single-component molecular conductor by utilizing strong hydrogen-bonding interactions between tetrathiafulvalene-based electron-donor molecules. These conductors are composed of highly symmetric molecular units constructed by the strong intra-unit hydrogen bond. Moreover, we demonstrate that, in this system, charge carriers are produced by the partial oxidation of the donor molecules and delocalized through the formation of the symmetric intra-unit hydrogen bonds. As a result, our conductors show the highest room-temperature electrical conductivity and the metallic state under the lowest physical pressure among the purely organic single-component systems, to our knowledge.

Charge-order driven proton arrangement in a hydrogen-bonded charge-transfer complex based on a pyridyl-substituted TTF derivative.

A unique N(+)-H···N hydrogen-bonded (H-bonded) dimer motif based on partially oxidized pyridyl-substituted TTF was constructed in the charge-transfer complex. The charge ordering in the TTF column by the charge disproportionation in the dimer regulates the arrangement of the H-bonded proton, evidencing the proton-electron coupled state.

Tuning of the ionization potential of paddlewheel diruthenium(II, II) complexes with fluorine atoms on the benzoate ligands.

A series of paddlewheel diruthenium(ii, ii) complexes with various fluorine-substituted benzoate ligands were isolated as THF adducts and structurally characterized: [Ru(2)(F(x)PhCO(2))(4)(THF)(2)] (F(x)PhCO(2)(-) = o-fluorobenzoate, o-F; m-fluorobenzoate, m-F; p-fluorobenzoate, p-F; 2,6-difluorobenzoate, 2,6-F(2); 3,4-difluorobenzoate, 3,4-F(2); 3,5-difluorobenzoate, 3,5-F(2); 2,3,4-trifluorobenzoate, 2,3,4-F(3); 2,3,6-trifluorobenzoate, 2,3,6-F(3); 2,4,5-trifluorobenzoate, 2,4,5-F(3); 2,4,6-trifluorobenzoate, 2,4,6-F(3); 3,4,5-trifluorobenzoate, 3,4,5-F(3); 2,3,4,5-tetrafluorobenzoate, 2,3,4,5-F(4); 2,3,5,6-tetrafluorobenzoate, 2,3,5,6-F(4); pentafluorobenzoate, F(5)). By adding fluorine atoms on the benzoate ligands, it was possible to tune the redox potential (E(1/2)) for [Ru(2)(II,II)]/[Ru(2)(II,III)](+) over a wide range of potentials from -40 mV to 350 mV (vs. Ag/Ag(+) in THF). 2,3,6-F(3), 2,3,4,5-F(4), 2,3,5,6-F(4) and F(5) were relatively air-stable compounds even though they are [Ru(2)(II,II)] species. The redox potential in THF was dependent on an electronic effect rather than on a structural (steric) effect of the o-F atoms, although more than one substituent in the m- and p-positions shifted E(1/2) to higher potentials in relation to the general Hammett equation. A quasi-Hammett parameter for an o-F atom (σ(o)) was estimated to be ∼0.2, and a plot of E(1/2)vs. a sum of Hammett parameters including σ(o) was linear. In addition, the HOMO energy levels, which was calculated based on atomic coordinates of solid-state structures, as well as the redox potential were affected by adding F atoms. Nevertheless, a steric contribution stabilizing their static structures in the solid state was present in addition to the electronic effect. On the basis of the electronic effect, the redox potential of these complexes is correlated to the HOMO energy level, and the electronic effect of F atoms is the main factor controlling the ionization potential of the complexes with ligands free from the rotational constraint, i.e. complexes in solution.