Suguru Maki

Redox-active tubular frameworks with TTF: self-assemblies by complementary hydrogen-bonds and π-stacks of TTF-phenyluracil

Tubular frameworks of a tetrathiafulvalene (TTF) based electron-donor with a N1-phenyluracil moiety were constructed by strong self-assembling abilities. The uracil moiety formed the reversed Watson–Crick type hydrogen-bond pair. The TTF moiety exhibited C–H⋯X hydrogen-bonds, S⋯S interactions, and uniform π-stack. The phenyl group formed a herring-bone array by the edge-to-face interaction. These multiple intermolecular interactions established channels of ca. 4 × 8 A. The cavities were filled with crystalline solvent molecules (tetrahydrofuran and pyridine), which were fixed on the framework by the C–H⋯X hydrogen-bonds.

Novel CT complexes of 4-hydroxyphenylthio-substituted TTFs with TCNQ or DDQ

Novel tetrathiafulvalene (TTF) derivatives with mono-, bis- and tetrakis(4-hydroxylphenylthio) groups as hydrogen-bonding functionality, 1-3, were prepared from the lithiated TTF and a diphenyldisulfide derivative. Room-temperature resistivities of compressed pellets for 1-DDQ, 2-DDQ and 2-TCNQ were 1.1 x 10 9 , 3.8 x 10 7 and 7.8 x 10 4 Ωcm, respectively. In these complexes, alternated stacking type structures were inferred from the electronic spectra.

Complementary double hydrogen-bonded CT complexes of TTF having uracil moiety ☆

Abstract We designed and prepared a TTF derivative with N 1 - n -butyl-substituted uracil (T n bU) which has the complementary double hydrogen-bonding (HB) sites and high solubility toward common organic solvents. The cyclic voltammogram of T n bU in DMF exhibited two-stage one-electron reversible oxidation behavior ( E 1 =−0.102 V ; E 2 =+0.095 V versus Fc/Fc + ), indicating slightly higher donating ability compared with TTF itself. The crystal structure of T n bU consists of the π-stacking dimer between TTF moieties and complementary double HB dimer between uracil moieties. The CT complex of T n bU with cyananilic acid (H 2 CNAL) exhibited alternated stacking type structure and complementary double HB between uracil moiety of T n bU and monoanion of H 2 CNAL, hydrogen cyananilate (HCNAL).

Synthesis of New 2,7-Diiodo-1,6-dithiapyrene and Crystal Structures of its Charge-Transfer Salts

We have designed and synthesized 2,7-diiodo-1,6-dithiapyrene (DIDTPY) as a first halogenated DTPY derivative. The X-ray structural analyses showed that the charge-transfer salts, (DIDTPY)(PF 6 ) and (DIDTPY) 1.5 (AuBr 2 ), possessed dimeric pairs of the cationic donor molecules and columnar stack of donor molecules, respectively. The conductivity of the compressed pellet for (DIDTPY) 1.5 (AuBr 2 ) exhibited a semiconducting behavior ( rt =2 2 10 m 2 Scm m 1 ). 1,6-dithiapyrene halogen-halogen interaction charge-transfer salt semiconductor dimensionality

Hydrogen-Bonded Open-Shell Molecules: Synthesis and Physical Properties of the Oxophenalenoxyl-Based Radical with Hydroxyl Group

As a new precursor for a hydrogen-bonded open-shell system, we have designed and synthesized 2,5,8-tri- tert -butyl-4,9-dihydroxyphenalenone 1 from commercially available 2,7-dimethoxynaphthalene in nine steps. The neutral radical generated from 1 with active PbO 2 exhibits higher stability compared with other 6-oxophenalenoxyl derivatives in the solid state. From the results of ESR and ENDOR/TRIPLE spectroscopies and MO calculations, the structure of the radical is identified to be monoradical 2 with a hydroxyl group.

New stable oxophenalenoxyl: Preparation and characterization of a 4-oxophenalenoxyl derivative

A 4-oxophenalenoxyl derivative, 2,5,8-tri- tert -butyl-4-oxophenalenoxyl, was prepared for the first time. This radical was successfully isolated in solid state. Its electronic spin structure was unequivocally characterized by means of liquid-phase ESR, ENDOR/TRIPLE measurements and DFT calculations. 4-oxophenalenoxyl 6-oxophenalenoxyl stable neutral radical ESR, ENDOR/TRIPLE spectra