A5036940557- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organoboron and organosilicon chemistry
- Crystallography and molecular interactions
- Molecular Junctions and Nanostructures
- Boron Compounds in Chemistry
- Luminescence and Fluorescent Materials
- Organic Electronics and Photovoltaics
- Surface Chemistry and Catalysis
- Synthesis and Properties of Aromatic Compounds
- Supramolecular Self-Assembly in Materials
- Supramolecular Chemistry and Complexes
- Synthesis and characterization of novel inorganic/organometallic compounds
- Catalytic Cross-Coupling Reactions
- Thermal properties of materials
- Organic Light-Emitting Diodes Research
- Conducting polymers and applications
- Porphyrin and Phthalocyanine Chemistry
- Graphene research and applications
- Boron and Carbon Nanomaterials Research
- Covalent Organic Framework Applications
- Advanced biosensing and bioanalysis techniques
- Advanced Thermoelectric Materials and Devices
- Metal-Organic Frameworks: Synthesis and Applications
- Fullerene Chemistry and Applications
Institute of Science Tokyo
2025
Tokyo Institute of Technology
2015-2024
Life Science Institute
2016-2024
SPring-8
2016-2020
RIKEN Advanced Science Institute
2010-2016
The University of Tokyo
2004-2010
Kyoto University
2010
Organ Technologies (Japan)
1990
Takasago (United States)
1988
Arylboronic esters can be used as versatile reagents in organic synthesis, represented by Suzuki–Miyaura cross-coupling. Here we report a serendipitous finding that simple arylboronic are phosphorescent the solid state at room temperature with lifetime on order of several seconds. The phosphorescence properties remarkable light general notion molecules require heavy atoms and/or carbonyl groups for efficient generation triplet excited state. Theoretical calculations phenylboronic acid...
Isomerism in covalent organic frameworks (COFs) has scarcely been known. Here, for the first time we show 3D COFs with three framework isomers or polymorphs constructed from same building blocks. All were obtained as large (>10 μm) crystals; although their crystal shapes distinctly different, they showed identical FT-IR and solid-state NMR spectra. Our structural analyses revealed unprecedented triple isomerism (noninterpenetrated dia, qtz, 3-fold interpenetrated dia-c3 nets). Furthermore,...
Standing at order Thin films of organic molecules on solid substrates tend to nucleate many sites and grow multiple domains. However, one large uniform film would be much more desirable in device applications. Seiki et al. designed that filled space a hexagonal tiling; propeller-like triptycene base adhered crystalline surfaces alkyl tails extended away from it. The authors could make well-ordered multilayer up centimeter length scales. Science , this issue p. 1122
Abstract C–C bond coupling reactions illustrate the wealth of organic transformations, which are usually mediated by organotransition metal complexes. Here, we show that a borafluorene with B–Cl moiety can mediate sequential alkyne insertion (1,2-carboboration) and deborylation/C sp 2 –C reactions, leading to aromatic molecules. The first step, affords borepin derivative, proceeds very efficiently between various alkynes simply mixing these two components. second step is triggered...
ConspectusThe design of properties and functions molecular assemblies requires not only a proper choice building blocks but also control over their packing arrangements. A highly versatile unit in this context is particular type triptycene with substituents at the 1,8,13-positions, called tripodal triptycene, which offers predictable multiple functionalization sites, both opposite 4,5,16- or 10 (bridgehead)-positions. These are capable two-dimensional (2D) nested hexagonal packing, leading...
Higher fullerenes (>/=C76) were selectively extracted from a fullerene mixture obtained combustion-based industrial production source by cyclic dimers of beta-unsubstituted porphyrin zinc complexes 2C5-2C7 with C5-C7 alkylene spacers as host molecules. Results single extraction the together beta-substituted analogue 2C6 (1C6) and spectroscopic titration 1C6 C60, C70, C96 indicated that selectivity toward higher is much dependent on structure units size cavity. Sequential three-stage...
Diborane(6) as a H-bridged dimer of monoborane can be converted cleanly by two-electron reduction into diborane(6) dianion, which is isoelectronic with ethane, through B-B σ-bond formation when each boron atom has bulky ligand on it. The existence the σ bond supported X-ray molecular structure [B-B length 1.924(3) Å], NMR studies, magnetic susceptibility measurements, and DFT calculations. Stepwise hydride abstraction reactions dianion produce corresponding diborane(5) anion doubly...
Abstract A series of octa-R-substituted bromo-s-hydrindacenes, “Rind-Br,” have been synthesized by a sequence the Lewis acid catalyzed intramolecular Friedel–Crafts reaction, bromination and vice versa. Their structural features physical properties depend on eight R-substituents at four benzylic positions s-hydrindacenyl skeleton. The molecular structures Rind-Br confirmed X-ray crystallography, indicating unique diversities bulky Rind groups.
The synthesis and assembly behavior of hexathioalkyl sumanenes, having a different feature surface electrostatic potential from non-substituted sumanene, are described.
When employing self-assembled monolayers (SAMs) for tuning surface and interface properties, organic molecules that enable strong binding to the substrate, large-area structural uniformity, precise alignment of functional groups, control their density are highly desirable. To achieve these goals, tripod systems bearing multiple bonding sites have been developed as an alternative conventional monodentate systems. Bonding all three has, however, hardly achieved, with consequence uniformity...
Experimental Raman spectra of molecularly doped P3HT thin films are combined with first-principles calculations on oligomer models to understand and identify the fingerprints for polarons bipolarons in P3HT.
In contrast to the common multiple bonding between carbon atoms, multiply bonded boron compounds have still been a synthetic challenge due electron deficiency of boron. We now report that stable doubly hydrogen-bridged diborane(4), EindB(mu-H)(2)BEind, is produced by two-electron oxidation hydrogen-substituted diborane(4) dianion [Li(+)(thf)](2)[Eind(H)BB(H)Eind](2-), where Eind denotes 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl. The X-ray crystallography reveals short B-B distance...
Optical resolution of nonsubstituted chiral fullerenes such as C(76) is one the most challenging subjects in host-guest chemistry. The novel cyclic host 1(2H), which bears a meso-diaryl-beta-octaethylporphyrin (P(2H)) unit on side and its N-2-acetoxyethyl derivative (P(N-EtOAc)) other, traps enantioselectively cavity furnishes 7% enantiomeric excess single extraction. Control experiments using reference hosts indicated importance high pi-basicity large asymmetric distortion N-substituted...
Tailoring structurally anisotropic molecular assemblies while controlling their orientation on solid substrates is an important subject for advanced technologies that use organic thin films. Here we report a supramolecular scaffold based tripodal triptycene assemblies, which enables functional units to assemble into highly oriented, multilayered two-dimensional (2D) structure substrates. The building block carries ethynyl group and three flexible side chains at the 10- 1,8,13-positions,...
Abstract Molecular doping allows enhancement and precise control of electrical properties organic semiconductors, is thus central technological relevance for (opto‐) electronics. Beyond single‐component molecular electron acceptors donors, salts have recently emerged as a promising class dopants. However, the pertinent fundamental understanding mechanisms capabilities limited. Here, unique salt consisting borinium cation (Mes 2 B + ; Mes: mesitylene) tetrakis(penta‐fluorophenyl)borate anion...
Molecules with tripodal anchoring to substrates represent a versatile platform for the fabrication of robust self-assembled monolayers (SAMs), complementing conventional monopodal approach. In this context, we studied adsorption 1,8,13-tricarboxytriptycene (Trip-CA) on Ag(111), mimicked by bilayer silver atoms underpotentially deposited Au. While SAMs frequently suffer from poor structural quality and inhomogeneous bonding configurations, triptycene scaffold featuring three carboxylic acid...
Upon inclusion complexation with a racemic mixture of chiral fullerene C76 ((+/-)-C76), novel cyclic host (1Rh) composed N-methylporphyrin (PNMe) and methylrhodium porphyrin (PRh) exhibited at 20 degrees C 1H NMR spectral profile diastereoisomerically split signals due to the NH group PNMe. In contrast, because faster guest exchange dynamics, metal-free reference 12H, under identical conditions, did not show any signature such diastereoisomeric splitting. Owing excellent resolution (15.6 Hz)...
Abstract The first isolable diborane(4) containing terminal B–H bonds, protected by the bulky 1,1,7,7-tetramethyl-3,3,5,5-tetrapropyl-s-hydrindacen-4-yl (MPind) groups, was synthesized as air- and moisture-sensitive colorless crystals. structure bonding nature of this H-terminal diborane(4), characterized X-ray crystallography, NMR studies, DFT calculations, were compared to those previously reported isomer, a doubly H-bridged butterfly-shaped bearing less...
Abstract Borinium ions, that is, two‐coordinate boron cations, are the most electron‐deficient isolable compounds. As borinium ions have only four formal valence electrons on boron, they should show a strong tendency to accept electron pairs atom fill its shell. Thus chemical reactions of expected give products in which coordination number is increased from two three or four. However, contrary this expectation, we found dimesitylborinium ion (Mes 2 B + ) undergoes twofold 1,2‐carboboration...
Induced-fit or conformational selection is of profound significance in biological regulation. Biological receptors alter their conformation to respond the shape and electrostatic surfaces guest molecules. Here we report a water-soluble artificial molecular host that can sensitively size, shape, charged state The host, i.e. nanocube, an assembled structure consisting six gear-shaped amphiphiles (GSAs). This nanocube expand contract its size upon encapsulation neutral anionic molecules with...
Triptycene-based molecules represent a promising platform for tripodal monomolecular assembly on solid substrates. The versatility of the approach can be increased significantly if decoration assembled tripods by purpose-specific functional groups will possible. In this context, possibility click reaction between 10-ethynyl-substituted 1,8,13-trimercaptomethyltriptycene monolayer (EtTripS) Au(111) and an azide-decorated substituent is tested additionally verified subsequent derivatization...
The first crystallographic and electron density distribution analyses of a thioaroyl cation unveil its true structural perspective; this chemical species can be mainly expressed as the combination thioketene form (II) sulfonium (III) with C≡S(+) triple bond character.