Formation of Nanometer-Thick Water Layer at High Humidity on Dynamic Crystalline Material Composed of Multi-Interactive Molecules

Crystalline powders self-assembled from interactive discrete molecules reversibly transformed from a porous structure to a 2D one with a nanometer-thick H2O layer by hydration/dehydration. Multi-point weak intermolecular interactions contributed to maintenance of each phase. This structure transformation induced a humidity-dependent ion conductivity change from insulator to 3.4 x 10(-3) S cm(-1).open1122sciescopu

Biased Bowl-Direction of Monofluorosumanene in the Solid State

Yakiyama Y., Li M., Zhou D., et al. Biased Bowl-Direction of Monofluorosumanene in the Solid State. Journal of the American Chemical Society 146, 5224 (2024); https://doi.org/10.1021/jacs.3c11311.A new curved π-conjugated molecule 1-fluorosumanene (1) was designed and synthesized that possesses one fluorine atom on the benzylic carbon of sumanene. This compound can exhibit bowl inversion in solution, leading to the formation of two diastereomers, 1endo and 1exo, with different dipole moments. Experimental and theoretical investigation revealed an energetical relationship among 1exo, 1endo, and solvent to realize the various endo:exo ratios in the single crystals of 1 depending on the crystallization solvent. Significantly, the molecular dynamics (MD) simulations revealed that 1exo positively worked for the elongation of the stacking structure and the final endo:exo ratio was affected by the relative stability difference between 1endo and 1exo derived by solvation. Such an arrangeable endo:exo ratio of 1 realized the preparation of unique materials showing a different dielectric response from the same molecule 1 just by changing the crystallization solvent

Design of a redox-active porous coordination network

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Design of rigid ligands for porous coordination networks

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Design of rigid porous coordination networks

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The Syntheses and Properties of Azaphenalene-Based Coordination Networks

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Dynamic Structure Transformation of a Porous Coordination Network Composed of New Tridentate Ligands

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Dynamic Structure Transformation of Kinetically Prepared TPHAP-Co(II) Porous Coordination Network

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Crystal surface mediated structure transformation of a kinetic framework composed of multi-interactive ligand TPHAP and Co(II)

A tripyridyl multi-interactive ligand TPHAP is prepared by a one-pot reaction on a gram scale. Network formation of Co(II) with TPHAP(-) gave kinetic and thermally more stable products. The kinetic network showed an unprecedented dynamic network transformation on the crystal surface by a ligand exchange reaction.open111013sciescopu

Partially Fluoride-Substituted Hydroxyapatite as a Suitable Support for the Gold-Catalyzed Homocoupling of Phenylboronic Acid: An Example of Interface Modification

Interface modification of hydroxyapatite-supported nanogold by fluoride ion improved the activity of the catalyst toward aerobic homocoupling of phenylboronic acid. In the aerobic homocoupling reaction of PhBF₃K catalyzed by hydroxyapatite-supported gold nanoclusters (Au:HAP), a study on the reactivity and reusability of the Au:HAP catalyst showed an unusual yield profile for the reaction. Intensive characterization of the catalyst by X-ray diffraction, transmission electron microscopy, and energy-dispersive X-ray spectroscopic analysis exhibited that the structure of the metal oxide support undergoes transformation from HAP to fluorapatite (FAP) and finally to calcium fluoride (CaF₂) during the course of these cycles of homocoupling of PhBF₃K. Investigations of the interactions of Au:HAP with PhBF₃K and of the fluoride ion-induced structural changes in both the support and the AuNCs, indicating that partially fluoride-substituted HAP (F-HAP) is the optimal support for the homocoupling of PhB­(OH)₂. This is effective both as a stabilizer for AuNCs through the phosphate moiety and in activation of C–B bond transmetalation through B–F interactions. The results strongly suggest that fine-tuning of the structure of the interface between metal clusters and their support (namely, surface modification) might be important in developing chemo-selective catalysts