Nagatoshi Koumura

Bio: Nagatoshi Koumura is an academic researcher from National Institute of Advanced Industrial Science and Technology. The author has contributed to research in topics: Carbazole & Dye-sensitized solar cell. The author has an hindex of 34, co-authored 93 publications receiving 6642 citations. Previous affiliations of Nagatoshi Koumura include University of Tsukuba & University of Groningen.

Light-driven monodirectional molecular rotor

Abstract: Attempts to fabricate mechanical devices on the molecular level1,2 have yielded analogues of rotors3, gears4, switches5, shuttles6,7, turnstiles8 and ratchets9. Molecular motors, however, have not yet been made, even though they are common in biological systems10. Rotary motion as such has been induced in interlocked systems11,12,13 and directly visualized for single molecules14, but the controlled conversion of energy into unidirectional rotary motion has remained difficult to achieve. Here we report repetitive, monodirectional rotation around a central carbon–carbon double bond in a chiral, helical alkene, with each 360° rotation involving four discrete isomerization steps activated by ultraviolet light or a change in the temperature of the system. We find that axial chirality and the presence of two chiral centres are essential for the observed monodirectional behaviour of the molecular motor. Two light-induced cis-trans isomerizations are each associated with a 180° rotation around the carbon–carbon double bond and are each followed by thermally controlled helicity inversions, which effectively block reverse rotation and thus ensure that the four individual steps add up to one full rotation in one direction only. As the energy barriers of the helicity inversion steps can be adjusted by structural modifications, chiral alkenes based on our system may find use as basic components for ‘molecular machinery’ driven by light.

Alkyl-functionalized organic dyes for efficient molecular photovoltaics.

Abstract: We designed and synthesized new alkyl-functionalized organic dyes, MK-1 and MK-2, for dye-sensitized solar cells (DSSCs). Based on the MK-2 dye, a high performance of efficiency (eta, 7.7%; short-circuit current density Jsc = 14.0 mA cm-2, open-circuit voltage Voc = 0.74 V, and fill factor FF = 0.74) was achieved under AM 1.5 G irradiation (100 mW cm-2). Remarkably, the relatively higher Voc for DSSCs based on MK-1 and MK-2 dyes, which have long alkyl chains, were observed among the organic dyes caused by the increasing of the electron lifetime in the conduction band of TiO2. Our molecular design of alkyl-functionalized dyes strongly suggests the promising performance of molecular photovoltaics based on organic dyes.

Hexylthiophene-Functionalized Carbazole Dyes for Efficient Molecular Photovoltaics: Tuning of Solar-Cell Performance by Structural Modification

Abstract: Novel organic dyes (MK dyes), which have a carbazole derivative as an electron donor and a cyanoacrylic acid moiety (═C(—C≡N)COOH) as an electron acceptor and an anchoring group, connected with n-hexyl-substituted oligothiophenes as a π-conjugated system, were designed and synthesized for application in dye-sensitized solar cells (DSSCs), which are one of the promising molecular photovoltaics. The photovoltaic performance of the DSSCs based on MK dyes markedly depends on the molecular structure of the dyes in terms of the number and position of n-hexyl chains and the number of thiophene moieties. Retardation of charge recombination caused by the existence of n-hexyl chains linked to the thiophene groups resulted in an increase in electron lifetime. As a consequence, an improvement of open-circuit photovoltage (Voc) and hence the solar-to-electric power conversion efficiency (η) of DSSCs was achieved upon addition of n-hexyl chains to the thiophene groups. In addition, the adsorption condition (amount of d...

Unidirectional molecular motor on a gold surface

Abstract: Molecules capable of mimicking the function of a wide range of mechanical devices have been fabricated, with motors that can induce mechanical movement attracting particular attention1,2. Such molecular motors convert light or chemical energy into directional rotary or linear motion2,3,4,5,6,7,8,9,10, and are usually prepared and operated in solution. But if they are to be used as nanomachines that can do useful work, it seems essential to construct systems that can function on a surface, like a recently reported linear artificial muscle11. Surface-mounted rotors have been realized and limited directionality in their motion predicted12,13. Here we demonstrate that a light-driven molecular motor capable of repetitive unidirectional rotation14 can be mounted on the surface of gold nanoparticles. The motor design14 uses a chiral helical alkene with an upper half that serves as a propeller and is connected through a carbon–carbon double bond (the rotation axis) to a lower half that serves as a stator. The stator carries two thiol-functionalized ‘legs’, which then bind the entire motor molecule to a gold surface. NMR spectroscopy reveals that two photo-induced cis-trans isomerizations of the central double bond, each followed by a thermal helix inversion to prevent reverse rotation, induce a full and unidirectional 360° rotation of the propeller with respect to the surface-mounted lower half of the system.

Second Generation Light-Driven Molecular Motors. Unidirectional Rotation Controlled by a Single Stereogenic Center with Near-Perfect Photoequilibria and Acceleration of the Speed of Rotation by Structural Modification

Abstract: Nine new molecular motors, consisting of a 2,3-dihydro-2-methylnaphtho[2,1-b]thiopyran or 2,3-dihydro-3-methylphenanthrene upper part and a (thio)xanthene, 10,10-dimethylanthracene, or dibenzocycloheptene lower part, connected by a central double bond, were synthesized. A single stereogenic center, bearing a methyl substituent, is present in each of the motors. MOPAC93-AM1 calculations, NMR studies, and X-ray analysis revealed that these compounds have stable isomers with pseudoaxial orientation of the methyl substituent and less-stable isomers with pseudoequatorial orientation of the methyl substituent. The photochemical and thermal isomerization processes of the motors were studied by NMR and CD spectroscopy. The new molecular motors all show two cis-trans isomerizations upon irradiation, each followed by a thermal helix inversion, resulting in a 360 degrees rotation around the central double bond of the upper part with respect to the lower part. The direction of rotation is controlled by a single stereogenic center created by the methyl substituent at the upper part. The speed of rotation, governed by the two thermal steps, was adjusted to a great extent by structural modifications, with half-lives for the thermal isomerization steps ranging from t(1/2)(theta) 233-0.67 h. The photochemical conversions of two new motors proceeded with near-perfect photoequilibria of 1:99.

Dye-Sensitized Solar Cells

Abstract: Dye-sensitized solar cells (DSCs) offer the possibilities to design solar cells with a large flexibility in shape, color, and transparency. DSC research groups have been established around the worl ...

Metal-Free Organic Dyes for Dye-Sensitized Solar Cells: From Structure: Property Relationships to Design Rules

Abstract: Dye-sensitized solar cells (DSSC) have attracted considerable attention in recent years as they offer the possibility of low-cost conversion of photovoltaic energy This Review focuses on recent advances in molecular design and technological aspects of metal-free organic dyes for applications in dye-sensitized solar cells Special attention has been paid to the design principles of these dyes and on the effect of various electrolyte systems Cosensitization, an emerging technique to extend the absorption range, is also discussed as a way to improve the performance of the device In addition, we report on inverted dyes for photocathodes, which constitutes a relatively new approach for the production of tandem cells Special consideration has been paid to the correlation between the molecular structure and physical properties to their performance in DSSCs

Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage.

Abstract: The area of transition-metal-catalyzed direct arylation through cleavage of CH bonds has undergone rapid development in recent years, and is becoming an increasingly viable alternative to traditional cross-coupling reactions with organometallic reagents In particular, palladium and ruthenium catalysts have been described that enable the direct arylation of (hetero)arenes with challenging coupling partners—including electrophilic aryl chlorides and tosylates as well as simple arenes in cross-dehydrogenative arylations Furthermore, less expensive copper, iron, and nickel complexes were recently shown to be effective for economically attractive direct arylations

Synthetic molecular motors and mechanical machines.

Abstract: The widespread use of controlled molecular-level motion in key natural processes suggests that great rewards could come from bridging the gap between the present generation of synthetic molecular systems, which by and large rely upon electronic and chemical effects to carry out their functions, and the machines of the macroscopic world, which utilize the synchronized movements of smaller parts to perform specific tasks. This is a scientific area of great contemporary interest and extraordinary recent growth, yet the notion of molecular-level machines dates back to a time when the ideas surrounding the statistical nature of matter and the laws of thermodynamics were first being formulated. Here we outline the exciting successes in taming molecular-level movement thus far, the underlying principles that all experimental designs must follow, and the early progress made towards utilizing synthetic molecular structures to perform tasks using mechanical motion. We also highlight some of the issues and challenges that still need to be overcome.