桝 飛雄真

Abstract Here, an unprecedented phenomenon in which 7‐coordinate lanthanide metallomesogens, which align via hydrogen bonds mediated by coordinated H₂O molecules, form micellar cubic mesophases at room temperature, creating body‐centered cubic (BCC)‐type supramolecular spherical arrays, is reported. The results of experiments and molecular dynamics simulations reveal that spherical assemblies of three complexes surrounded by an amorphous alkyl domain spontaneously align in an energetically stable orientation to form the BCC structure. This phenomenon differs greatly from the conventional self‐assembling behavior of 6‐coordinated metallomesogens, which form columnar assemblies due to strong intermolecular interactions. Since the magnetic and luminescent properties of different lanthanides vary, adding arbitrary functions to spherical arrays is possible by selecting suitable lanthanides to be used. The method developed in this study using 7‐coordinate lanthanide metallomesogens as building blocks is expected to lead to the rational development of micellar cubic mesophases.

The metal–insulator transition induced by the gate electric field in the charge order phase of the α-(BEDT-TTF)2I3 single-crystal field-effect transistor (FET) structure was clearly observed near the phase transition temperature. An abrupt increase in the electrical conductance induced by the applied gate electric field was evident, which corresponds to the partial dissolution of the charge order phase triggered by the gate electric field. The estimated nominal dissolved charge order region (i.e., the gate-induced metallic region) was overestimated in 130–150 K, suggesting additional effects such as Joule heating. On the other hand, in the lower temperature region below 120 K, the corresponding dissolved charge order was several monolayers of BEDT-TTF, suggesting that it is possible to dissolve the charge order phase within the bistable temperature region.

The seven-coordinate Ho(III) aqua-tris(dibenzoylmethane)(DBM) complex, referred to as Ho-(DBM)3·H2O, was first reported in the late 1960s. It has a threefold symmetric structure, with Ho at the center of three dibenzoylmethane ligands and hydrogen-bonded water to ligands. It is considered that the hydrogen bonds between the water molecule and the ligands surrounding Ho play an important role in the formation of its symmetrical structure. In this work, we developed new force-field parameters for classical molecular dynamics (CMD) simulations to theoretically elucidate the structure and dynamics of Ho-(DBM)3·H2O. To develop the force field, structural optimization and molecular dynamics were performed on the basis of ab initio calculations using the plane-wave pseudopotential method. The force-field parameters for CMD were then optimized to reproduce the data obtained from ab initio calculations. Validation of the developed force field showed good agreement with the experimental crystalline structure and ab initio data. The vibrational properties of water in Ho-(DBM)3·H2O were investigated by comparison with bulk liquid water. The vibrational motion of water was found to have a characteristic mode originating from stationary rotational motion along the c-axis of Ho(III) aqua-tris(dibenzoylmethane). Contrary to expectations, the hydrogen-bond dynamics of water in Ho-(DBM)3·H2O were found to be almost equivalent to those of bulk liquid water except for librational motion. This development route for force-field parameters for CMD and the establishment of water dynamics can advance the understanding of water-coordinated metal complexes with high coordination numbers such as Ho-(DBM)3·H2O.