Showing papers by "Takashi Kubo published in 2021"

Long Carbon-Carbon Bonding beyond 2 Å in Tris(9-fluorenylidene)methane.

Abstract: We report on our investigation of C-C bonding longer than 2.0 A, which can be realized by perpendicularly facing two fluorenyl rings in the title compound. A small orbital overlap between the distantly positioned carbon atoms is observed as a small concentration of electrons on the X-ray electron density map. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the compound originate from the in-phase and out-of-phase interactions of the overlapping orbitals, respectively, with a gap of 2.39 eV. Solid-state 13C NMR spectroscopy shows a sharp peak at 82.9 ppm for the long-bonded carbons, and a CASSCF(6,6) calculation indicates small diradical character. The experimental and theoretical analyses reveal sufficient covalent-bonding interaction in the long-bonded carbon pair.

Synthesis of Anthracene-Based Cyclic π-Clusters and Elucidation of their Properties Originating from Congested Aromatic Planes

Abstract: Synthesis and properties of anthracene-based cyclic π-clusters which possess two and four anthracene units are discussed. The optimal cyclization conditions were determined based on a nickel(0)-mediated reaction that afforded a cyclic anthracene dimer as the major product. Bringing two anthracene planes in close proximity in a face-to-face manner resulted in red-shifted absorption owing to the narrowing of the HOMO-LUMO gap. The cyclic anthracene dimer exhibits multi-stimuli responsiveness due to high π-congestion. For example, photoirradiation on the anthracene dimer affords its photoisomer having C-C bonds that are longer than 1.65 A, which can undergo thermal reversion under gentle heating. This enabled mechanochromism of the photoisomer (colorless) to the original anthracene dimer (red). Photoisomerization was also observed in the crystalline state, accompanied by crystal jumping or collapsing, that is, the photosalient effect.

Syntheses and Properties of Open-Shell π-Conjugated Molecules

Abstract: Organic compounds with an open-shell electronic structure, in which unpaired electrons remain in the molecule, have attracted much attention in recent years due to their high reactivity and unique ...

Biradicaloid Behavior of a Twisted Double Bond.

Abstract: A compound with a highly twisted C═C bond in the intermediate bond dissociation region was isolated, and its biradicaloid nature was experimentally demonstrated. A bianthrone derivative substituted with long-chain alkoxy groups was synthesized, and its twisted conformer was assembled into crystals through hydrophobic intermolecular interactions of the introduced alkoxy chains. X-ray crystallography revealed that the C═C bond connecting the two anthrone rings has a long bond length (1.429 A) and a large torsional angle (57.33°). In addition, ESR studies revealed that the twisted bianthrone has biradicaloid character with a small singlet-triplet energy gap of 23.8 kJ mol-1. The thermally excited triplet species were observed in the ESR spectrum as distinct fine structures along with a ΔMS = ±2 forbidden transition.

Optical nature of non-substituted triphenylmethyl cation: Crystalline state emission, thermochromism, and phosphorescence

Abstract: Since the discovery of the triphenylmethyl (trityl) cation 120 years ago, a variety of aromatic cations having various colors and luminescence properties have been rigorously studied. Many, differently substituted trityl cations have been synthesized and their optical properties have been elucidated. However, the optical properties of the parent, non-substituted and highly reactive trityl cation, which was observed to be very weakly luminescent, have not been subjected to detailed investigation. In the effort described herein, we explored the optical nature of non-substituted trityl hexafluorophosphate (PF6) in the crystalline state. Trityl PF6 was found to exist as two crystal polymorphs including a yellow (Y) and an orange (O) form. Moreover, we observed that these crystalline forms display crystalline-state emission with different colors. The results of X-ray crystallographic analysis showed that the two polymorphs have totally different molecular packing arrangements. Furthermore, an investigation of their optical properties revealed that the O-crystal undergoes a distinct color change to yellow upon cooling as a consequence of a change in the nature of the charge transfer interaction between the cation and PF6 anion, and that both the Y and O crystal exhibit phosphorescence.

Observation of new neutron-rich isotopes in the vicinity of Zr 110

Abstract: Neutron-rich radioactive isotope (RI) beams in the vicinity of Zr110 were produced using the in-flight fission of a 345-MeV/nucleon U238 beam at the RIKEN Radioactive Isotope Beam Factory. The RI beams were separated in flight by the large-acceptance two-stage fragment separator BigRIPS. Isotopes were clearly identified in a low-background particle-identification plot, which was obtained from the measurements of time of flight, magnetic rigidity, and energy loss using beam-line detectors placed in the BigRIPS separator and the ZeroDegree spectrometer. Nine new isotopes, Br101, Kr102, Rb105,106, Sr108, Y110,111, Zr114, and Nb117, are reported for the first time, with their measured production cross sections compared with the extrapolations of lighter isotopes down to the femtobarn regime.

Synthesis and Properties of Fused Extended Tetrathiafulvalene Donors with Dithienylmethylene Spacer and Application to Organic Rechargeable Batteries

Abstract: Several derivatives of 1,3-dithiole[3]dendralene derivatives with two thiophene spacers (2) were synthesized. The results of an X-ray structure analysis of an analog without fused TTF units and a D...

Spin-Spin Interactions in One-Dimensional Assemblies of a Cumulene-Based Singlet Biradical.

Abstract: The synthesis of phenalenyl-endcapped [5]cumulene as a cumulene-based singlet biradical and the spin correlation changes of one-dimensional aggregates are described. The high propensity for self-aggregation of phenalenyl rings and the introduction of bulky substituents into the appropriate positions led to the formation of a one-dimensional chain assembly. Single-crystal X-ray structural analysis indicated that the bond length alternation of the cumulene chain increased with decreasing temperature, along with improved overlapping of the phenalenyl rings. Variable-temperature Raman spectroscopy and magnetic susceptibility measurements revealed that a localized spin pair within the molecule decouples at low temperatures, and a continuum spin system involving intra- and intermolecular spin-spin interactions emerges in the one-dimensional chain.

Nature of a Long Carbon–Carbon Bond Beyond 2.0 Å

Abstract: Elongating carbon–carbon (C–C) single bonds is challenging in terms of molecular design and synthesis, and in understanding the nature of the long bonds. Herein, we demonstrate that a C–C bond longer than 2.0 Å can be realised by face-to-face interactions between fluorenyl rings. A small orbital overlap between the distantly positioned carbon atoms is observed as a small concentration of electrons on the X-ray electron density maps. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the compound originate from the in-phase and out-of-phase interactions of the overlapping orbitals, respectively, with a gap of 2.39 eV. Solid-state 13C NMR spectroscopy shows a sharp peak at 82.9 ppm for the long-bonded carbons, while a CASSCF(6,6) calculation indicates a small diradical character. The experimental and theoretical analyses reveal a sufficient covalent bonding character in the long C–C bond.