Ryohei Kurata

Isolation and Characterization of Persistent Radical Cation and Dication of 2,7-Bis(dianisylamino)pyrene

Orbital interaction between 2,7-pyrenylene and two nitrogen redox-active centers effectively reduces the energy difference between HOMO and HOMO-1, both of which were distributed over the two nitrogen centers. In fact, one- and two-electron oxidation of 2,7-bis(dianisylamino)pyrene 3 generated a persistent radical cation and a persistent dication, respectively, and we succeeded in the isolation and single crystal X-ray structural analyses of all three oxidation states. The radical cation was considered as a spin and charge delocalized mixed-valence compound with a semiquinoidal structure. The dication was in an open-shell singlet state with a small singlet-triplet energy gap. The molecular and electronic structures for all three oxidation states of 3 were studied in comparison with the data reported for each oxidation state of closely related bis(triarylamine)s, of which structures were determined by X-ray crystallography.

Diarylamino- and Diarylboryl-Substituted Donor–Acceptor Pyrene Derivatives: Influence of Substitution Pattern on Their Photophysical Properties

Dianisylamino donor (D) and dimesitylboryl acceptor (A) substituents were introduced at the 1,6- and 2,7-positions of pyrene to demonstrate that the substitution patterns influence the photophysical properties. The different pictures in orbital interactions between the pyrene core and the D-A substituents led to the outcome that 1,6-substituted pyrene derivative 1 had stronger electron-donating and electron-accepting properties in conjunction with a small HOMO-LUMO gap, as compared to the 2,7-substituted derivative. For these pyrene derivatives, modest (ΦF = 0.2) to strong (ΦF = 1.0) fluorescence was detected in degassed organic solvents; 1 exhibited a typical intramolecular charge transfer (ICT) emission obeying energy-gap law, while 2 displayed a moderate inverse energy-gap law, originating from the different substitution patterns. Although theoretical calculations predicted that both 1 and 2 adopt highly twisted ICT excited states (TICT excited states) even in the gas phase, but practically, it was suggested that the observed photophysical properties could be determined by the extent of twist angle of the TICT-like excited state in accordance with the solvent polarity. Moreover, the bulky D-A substituents inhibit the intermolecular direct π-π interactions, thereby resulting in the bright and moderate solid-state emissions for 1 (ΦF = 0.76) and 2 (ΦF = 0.21), respectively.

Redox modulation of para-phenylenediamine by substituted nitronyl nitroxide groups and their spin states.

Three kinds of para-phenylenediamine (PDA) derivatives bearing nitronyl nitroxide (NN) groups were prepared and characterized on the basis of the electrochemical, electron spin resonance (ESR) spectroscopic, absorption spectroscopic, and magnetic susceptibility measurements. It was clarified that the oxidation potential of the central PDA unit is strongly influenced by the numbers of substituted electron-withdrawing NN groups. In addition, the intervalence charge transfer in the central PDA unit was detected in the monocationic states of the PDAs with two NN groups, indicating the coexistence of the localized spins and the delocalized spin on theses molecules. Moreover, pulsed ESR measurements confirmed that the delocalized spin on the central PDA unit and the localized two spins on the NN groups were ferromagnetically coupled in the monocationic states.

Tetraaza[1.1.1.1]m,p,m,p-cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes

Diradical dications of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene (1) and 9,10-anthracenylene (2a) moieties are embedded in their macrocyclic backbones were successfully isolated as air-stable salts. The structures of 12+ and 2a2+ were elucidated by X-ray analysis, and significantly different types of structural deformation led to different spin density distributions due to the steric demand of the confronted arene moieties. The singlet-triplet energy gaps were determined to be +0.3 kcal mol-1 (+151 K) and -1.0 kcal mol-1 (-503 K) by SQUID measurements, indicating the triplet ground state for 12+ and the singlet ground state for 2a2+.

Isolable Triradical Trication of Hexaaza[16]paracyclophane with Embedded 9,10-Anthrylenes: A Frustrated Three-Spin System

A new derivative of hexaaza[16]paracyclophane in which p-phenylenes are alternately replaced by 9,10-anthrylenes was prepared to investigate the impact on overall π-conjugation as well as conformational change of the macrocycle. The charge and spin distribution for one-electron and three-electron oxidation of the macrocycle was elucidated by means of electrochemical, spectroelectrochemical, EPR spectroscopic, and SQUID magnetometric methods. In particular, the triradical trication was successfully isolated as an air-stable salt, and moreover, its structure was disclosed by X-ray analysis. The triradical trication was characterized as a spin-frustrated three-spin system with the antiferromagnetic exchange interaction (J/kB ≃ - 74 K).

Diazadibora[1.1.1.1]m,p,m,p‐cyclophanes: Ambipolar Conjugated Macrocycles with Different B–π–N Embedded Patterns

Are different B(boron)-π-N(nitrogen) embedded patterns to bring about significant different (opto)electronic properties for the same macrocyclic molecular backbone? A series of B-π-N-embedded alternate-meta-para-linked cyclophanes 1-3 have been prepared and characterized as a new class of ambipolar π-conjugated B-π-N macrocycles. The answer to the opening question is yes. These macrocycles revealed the intramolecular charge transfer in the oxidized states and the intriguing photophysical proprerties in accordance with the embedded patterns, suggesting the electronic structures are tunable by introducing multiple B-π-N moieties.

Modulation of Open-shell Characters of Amine-inserted Diphenoquinones via Structural Modification

In this study, a series of triphenylamine derivatives with two 2,6-diphenylphenoxy radicals (2 a-d), which could be regarded as amine-inserted diphenoquinones have been synthesized and investigated their structures and electronic properties. The structures of 2 a-d were confirmed by single-crystal X-ray analysis, showing the characteristic bond length alternation patterns for closed-shell quinoids. The solutions of 2 a-d exhibited clear ESR signals even at room temperature, indicating their thermally accessible diradical states. The NMR and ESR measurements showed that the diradical character of 2 a-d were increased in the order of 2 a<2 b<2 c<2 d, well-reproduced by theoretical calculations. The results of this work strongly suggest that the diradical character of this class of compounds could be tuned by changing the substituent on the central nitrogen atom.