The University of Osaka · Materials Science
Professor Yosuke Tani's research lab specializes in the development of innovative catalytic transformations involving carbon dioxide and silicon-based reagents, with a focus on regio- and stereoselective synthesis of complex organic molecules. The lab explores copper-catalyzed reactions for the efficient conversion of CO2 into valuable building blocks such as carboxylated silanes and homoallylic alcohols, leveraging hydrosilanes as mild reductants. A significant direction involves the design of metal-free organic semiconductors that exhibit unique photophysical properties, including room-temperature phosphorescence and mechanochromic behavior, particularly through intramolecular chalcogen bonding and crystal engineering. The lab also investigates photo-responsive materials, such as heteroaromatic 1,2-diketones, that undergo light-induced crystal-to-liquid transitions with tunable luminescence, enabling dynamic optical responses.
Figures are computed from collected data and may differ slightly.
A regiodivergent silacarboxylation of allenes under a CO2 atmosphere with PhMe2Si-B(pin) as a silicon source in the presence of a copper catalyst at 70 °C has been developed. The regioselectivity of the reaction is successfully reversed by the proper choice of ligand; carboxylated vinylsilanes are obtained with rac-Me-DuPhos as the ligand, whereas the use of PCy3 affords carboxylated allylsilanes. Thus, two different carboxylated silanes can be selectively and regiodivergently synthesized from a
A highly selective carbon-carbon bond-forming transformation of carbon dioxide (CO2) to alcohol oxidation level has been disclosed. By employing a copper/bisphosphine catalyst system and hydrosilanes as mild and easy-to-handle reducing agents, various allenes can be reacted with CO2 to regioselectively obtain homoallylic alcohols. Esters and other reducible functionalities on the allenes remain intact during the reaction, whereas CO2 is reduced to alcohol oxidation level.
An organic 1,2-diketone with intramolecular chalcogen bonding overcomes the room-temperature phosphorescence (RTP) quenching problem on amorphization, representing the first RTP-to-RTP mechanochromism of a metal-free organic molecule.
Abstract The copper-catalyzed silylative allylation of ketones with allenes and silylboranes via an in situ generated β-silylallylcopper intermediate has been developed. Various ketones and allenes were converted to the homoallylic tertiary alcohols bearing internal (E)-vinylsilane moieties regio- and stereoselectively in good to high yields. Aldehydes were also employed as electrophiles in the reaction.
The room-temperature phosphorescence (RTP) of metal-free organic crystals is normally quenched by mechanical stimulation. Herein, we demonstrate the opposite mechanoresponse of turn-on RTP. A desymmetrization of a C<sub>2</sub>-symmetric 1,2-diketone creates space for molecular motion in the crystal, quenching the RTP from the crystal while maintaining that from the amorphous solid.
The phenomenon of crystal melting by light irradiation, known as photo-induced crystal-to-liquid transition (PCLT), can dramatically change material properties with high spatiotemporal resolution. However, the diversity of compounds exhibiting PCLT is severely limited, which hampers further functionalisation of PCLT-active materials and the fundamental understandings of PCLT. Here, we report on heteroaromatic 1,2-diketones as the new class of PCLT-active compounds, whose PCLT is based on conform
We report metal-free organic 1,2-diketones that exhibit fast and highly efficient room-temperature phosphorescence (RTP) with high colour purity under various conditions, including solutions. RTP quantum yields reached 38.2% in solution under Ar, 54% in a polymer matrix in air, and 50% in crystalline solids in air. Moreover, the narrowband RTP consistently dominated the steady-state emission, regardless of the molecular environment. Detailed mechanistic studies using ultrafast spectroscopy, sing
Achieving organic room-temperature phosphorescence (RTP) in a solvent-free liquid state is a challenging task because the liquid state provides a less rigid environment than the crystal. Here, we report that an unsymmetrical heteroaromatic 1,2-diketone forms an organic RTP liquid. This diketone exists as a kinetically stable supercooled liquid, which resists crystallisation even under pricking or shearing stresses, and remains as a liquid for several months. The unsymmetrical diketone core is fl
A rigid, polycyclic, and fully-ring-fused π-system without any rotatable substituents shows aggregation-induced emission or aggregation-caused quenching, depending on the fused aromatic rings.
A palladium-catalyzed double carbonylative cyclization of benzoins has been developed, which realizes the synthesis of bis-ester-bridged stilbenes just in two steps from aldehydes. Thus, the obtained fully fused tetracyclic π-systems have a pyrano[3,2- b]pyran-2,6-dione (PPD) core on their center, showing two reversible reductions at low potentials. In addition, their photoluminescence properties are strikingly affected by the aromatic rings fused to the PPD core; bis- thieno-fused PPDs are foun
Phosphorescence is a unique luminescence property with a number of advantages that are complementary to those of fluorescence. However, achieving efficient room-temperature phosphorescence (RTP) using metal-free organic molecules is a challenging task owing to the spin-forbidden nature of phosphorescence. Extensive research in the last decade has revealed that decent RTP can be obtained from organic crystals based on the suppression of nonradiative decay. Nonetheless, once the rigid crystalline
Liquid is the most flexible state of condensed matter and shows promise as a functional soft material. However, these same characteristics make it challenging to achieve efficient room-temperature phosphorescence (RTP) from metal-free organic molecular liquids. Herein, we report efficient RTP from liquefied thienyl diketones bearing one or two dimethyloctylsilyl (DMOS) substituents. These solvent-free liquids exhibit high RTP quantum yields up to 5.6% in air and 25.6% under Ar due to their large
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