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31.
Silacyclophanes possessing two disilanyl pillars were synthesized from tricyclic heteroarenes in one‐pot synthetic procedures. The step‐like anti structures of three congeners bearing two heteroarene units were revealed in single crystals by X‐ray crystallographic analysis. Depending on the structures of aromatic units, torsion angles at the disilanyl pillars altered to maintain the overall step‐like molecular structures. The structure, however, fluctuated between anti and syn conformers in a solution phase despite the presence of eight methyl groups on the ring periphery. The analysis of the coalescence temperature with NMR spectroscopy showed the fundamental energetics of the dynamics. The subtle structural differences affected the dynamic behavior of the silacyclophanes. 相似文献
32.
Koki Ikemoto Shotaro Harada Seungmin Yang Taisuke Matsuno Hiroyuki Isobe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202114305
A 3-nm molecule comprising a cylindrical core and cross-shaped rims was designed and synthesized by developing a modular synthetic route. By using a cyclic precursor from previous studies as a starting material, multiple carbazole units were installed at the rims of the defective cylinder. The defective cylinder was synthetically doped with two types of nitrogen atoms, that is, pyridinic and pyrrolic nitrogen atoms, which resulted in solvatochromic shifts in fluorescence by charge-transfer interactions. The structure of the large, C552H496N24 molecule was fully disclosed by crystallographic analyses, and the unique helical arrangement of nitrogen-doped cylinders in the crystal was revealed. 相似文献
33.
Dr. Guangwu Li Prof. Taisuke Matsuno Yi Han Dr. Hoa Phan Shaofei Wu Dr. Qing Jiang Ya Zou Prof. Hiroyuki Isobe Prof. Jishan Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9814-9822
Synthesis of fully conjugated cyclophanes containing large-size polycyclic aromatics is challenging. Now, three benzidine-linked, hexa-peri-hexabenzocoronene (superbenzene)-based ortho-, para-, and meta-cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre-organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine-linked cyclophanes. Their geometries were confirmed by X-ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine-linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet-triplet energy gap. Two enantiomers for the ortho-cyclophanes ( 1-NH and 1-N ) were isolated and their chiral figure-of-eight macrocyclic structures were identified. The cage-like cyclophanes 2-NH and 3-NH with concave surface can selectively encapsulate fullerene C70. 相似文献
34.
Guangwu Li Taisuke Matsuno Yi Han Hoa Phan Shaofei Wu Qing Jiang Ya Zou Hiroyuki Isobe Jishan Wu 《Angewandte Chemie (International ed. in English)》2020,59(24):9727-9735
Synthesis of fully conjugated cyclophanes containing large‐size polycyclic aromatics is challenging. Now, three benzidine‐linked, hexa‐peri‐hexabenzocoronene (superbenzene)‐based ortho‐, para‐, and meta‐cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre‐organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine‐linked cyclophanes. Their geometries were confirmed by X‐ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine‐linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet‐triplet energy gap. Two enantiomers for the ortho‐cyclophanes ( 1‐NH and 1‐N ) were isolated and their chiral figure‐of‐eight macrocyclic structures were identified. The cage‐like cyclophanes 2‐NH and 3‐NH with concave surface can selectively encapsulate fullerene C70. 相似文献
35.
Taisuke Matsuno Yusuke Nakai Yutaka Maniwa Maki Someya Sota Sato Hiroyuki Isobe 《化学:亚洲杂志》2020,15(2):273-278
In a tight host–guest complex assembled solely by nondirectional van der Waals forces, unique motions of the guest, such as solid‐state inertial rotations, emerge. The regulation of dynamic motions is an important element to be explored for novel functions of such complexes, which may be seemingly difficult to achieve because of the nondirectionality of the assembling forces. A regulated, single‐axis rotation was made possible by choosing an appropriate shape of the guest in the tubular host. Specifically, an ellipsoidal guest was made to stand along a cylinder axis of the host, which consequently resulted in single‐axis rotations of the guest in the solid. The rotational frequency was considerably high for solid‐state rotations but was suppressed to 10 GHz, which was 1/20 of the isotropic rotation of a spherical guest. In‐depth kinetic analyses quantitatively revealed that the entropy cost was a determining factor that regulated the dynamics. 相似文献
36.
37.
We revisited the vanadium oxide phosphors, AVO3 (A:K, Rb, and Cs) and M3V2O8 (A:Mg and Zn) for a revaluation of possibility of these compounds for lighting applications, and the internal quantum efficiency (η) and luminescent colour properties for AVO3 (A:K, Rb, and Cs) and M3V2O8 (A:Mg, and Zn) have been presented. The AVO3 showed the broadband emission from 380 to 800 nm, and the η for the KVO3, RbVO3 and CsVO3 were 4%, 79% and 87%, respectively. The CIE colour coordinates are located at white region on the chromaticity diagram. The M3V2O8 (A:Mg and Zn) also exhibited a quite broadband emission between 410 and 900 nm, indicating yellow luminescent colour. The Zn3V2O8 showed high η value, 52%, compared to that of the Mg3V2O8 (η=6%). This enhancement of η in the Zn3V2O8 could be due to the increasing exciton diffusion assisted by the hybridizations of Zn 3d and O 2p orbitals for the valence band, and Zn 4s and Ti 3d orbitals for the conduction band. 相似文献
38.
[structure: see text] 8,11-Dideoxytetrodotoxin, an unnatural tetrodotoxin analogue, was synthesized in a highly stereoselective manner from a common intermediate in our synthetic studies on tetrodotoxin. The synthesis features neighboring group participation of trichloroacetamide for stereoselective hydroxylation, protection of ortho ester, and guanidine installation with Boc-protected isothiourea. 相似文献
39.
We report the first observation of coherent magnetic excitations in a spin ladder system NaV2O5 by using femtosecond time-domain spectroscopy. A pronounced coherent oscillation is observed at 127 cm(-1) (nearly twice the spin gap energy) and assigned to a two-magnon bound state, based on the temperature dependence of the intensity below the charge ordering phase transition at T(C) = 34 K. This mode can be observable only when circularly polarized light is used as a pump or a probe beam, suggesting that it corresponds to a spin-flip excitation from the singlet ground state. A phonon mode strongly coupled to the spin state is also found at 303 cm(-1). 相似文献
40.