Kazunobu Sato

Organic tailored batteries materials using stable open-shell molecules with degenerate frontier orbitals

Secondary batteries using organic electrode-active materials promise to surpass present Li-ion batteries in terms of safety and resource price. The use of organic polymers for cathode-active materials has already achieved a high voltage and cycle performance comparable to those of Li-ion batteries. It is therefore timely to develop approaches for high-capacity organic materials-based battery applications. Here we demonstrate organic tailored batteries with high capacity by using organic molecules with degenerate molecular orbitals (MOs) as electrode-active materials. Trioxotriangulene (TOT), an organic open-shell molecule, with a singly occupied MO (SOMO) and two degenerate lowest-unoccupied MOs (LUMOs) was investigated. A tri-tert-butylated derivative ((t-Bu)(3)TOT)exhibited a high discharge capacity of more than 300 A h kg(-1), exceeding those delivered by Li-ion batteries. A tribrominated derivative (Br(3)TOT) was also shown to increase the output voltage and cycle performance up to 85% after 100 cycles of the charge-discharge processes.

Synthesis and Characterization of Teranthene: A Singlet Biradical Polycyclic Aromatic Hydrocarbon Having Kekulé Structures

A teranthene derivative has been successfully isolated in a crystalline form for the first time. Geometrical considerations and physical property investigations indicate that the molecule possesses prominent biradical character in the ground state.

Alternating covalent bonding interactions in a one-dimensional chain of a phenalenyl-based singlet biradical molecule having Kekulé structures.

A novel naphthoquinoid singlet biradical (2a) stabilized by phenalenyl rings is prepared by a multistep procedure and is investigated in terms of covalent bonding interactions. The molecule 2a gives single crystals, in which a 1D chain is formed with a very short π-π contact at the overlapping phenalenyl rings. The unpaired electrons in 2a are involved in covalent bonding interactions not only within the molecule but also between the molecules in the 1D chain, and a linear conjugation is made of the alternating intra- and intermolecular covalent bonding interactions through conventional π-conjugation and multicenter bonding, respectively. The linear conjugation causes a lower-energy shift of the optical transition band in the crystal, but the transition energy is higher than that of the benzoquinoid singlet biradical (1a). This optical behavior and the magnetic susceptibility measurements reveal that the intermolecular covalent bonding interaction in the 1D chain of 2a is greater in strength than the intramolecular one, despite the fact that a fully conjugated Kekulé structure can be drawn for 2a.

A Synthetic Two-Spin Quantum Bit: g-Engineered Exchange-Coupled Biradical Designed for Controlled-NOT Gate Operations†

A quantum gate: A system of two coupled electron spins that is useful for simple quantum computing operations has been prepared by synthesis of a biradical 1 and co-crystallization with an isomorphous host molecule. The two weakly exchange-coupled quantum bits (target qubit blue and control qubit red) span four electron spin states. The electron spin transition is denoted by two black arrows.

Nitroxide-substituted nitronyl nitroxide and iminonitroxide.

We report on the highly compact nitroxide-substituted nitronyl nitroxide 1 and iminonitroxide 2; they have isoelectronic structures with trimethylenemethane. These diradicals are stable under aerated conditions at room temperature and have large positive exchange interactions: J/k(B) = +390 K (H = -2JS(1)(/)(2)·S(1/2)) for 1 and J/k(B) ≈ +550 K for 2.

Synthesis, crystal structure, and physical properties of sterically unprotected hydrocarbon radicals.

We have prepared and isolated neutral polycyclic hydrocarbon radicals. A butyl-substituted radical gave single crystals, in which a π-dimeric structure, not a σ-bonded dimer, was observed, even though steric protection was absent. Thermodynamic stabilization due to the highly spin-delocalized structure contributes effectively to the suppression of σ-bond formation.

Spin-Orbit Contributions in High-Spin Nitrenes/Carbenes: A Hybrid CASSCF/MRMP2 Study of Zero-Field Splitting Tensors

Zero-field splitting (ZFS) tensors (D tensors) of organic high-spin oligonitrenes/oligocarbenes up to spin-septet are quantitatively determined on the basis of quantum chemical calculations. The spin-orbit contributions, D(SO) tensors are calculated in terms of a hybrid CASSCF/MRMP2 approach, which was recently proposed by us. The spin-spin counterparts, D(SS) tensors are computed based on McWeeny-Mizunos equation in conjunction with the RODFT spin densities. The present calculations show that more than 10% of ZFS arises from spin-orbit interactions in the high-spin nitrenes under study. Contributions of spin-bearing site-site interactions are estimated with the aid of a semi-empirical model for the D tensors and found to be ca. 5% of the D(SO) tensor. The analysis of intermediate states reveal that the largest contributions to the calculated D(SO) tensors are attributed to intra-site spin flip excitations and delocalized π and π* orbitals play an important role in the inter-site spin-orbit interactions.

A Bowl-Shaped ortho-Semiquinone Radical Anion: Quantitative Evaluation of the Dynamic Behavior of Structural and Electronic Features†

Organic radical ions play increasingly important roles in a wide range of research fields from biochemistry to materials science. o-Semiquinone is a typical organic radical anion with multistage redox ability that can form chelate salts and complexes with many kinds of metal cations. Investigation of a variety of transition-metal complexes of o-semiquinone radical could help not only to increase general knowledge of their fundamental chemistry but also to develop functional materials based on valence tautomerism phenomena. 3] In contrast, the alkali-metal salts have been extensively studied, and much attention has been focused on the dynamic behavior of their structure and of the electronic features of the ion pair in solution. 5] Solution-phase ESR spectroscopy measurements of some alkali-metal salts show significant temperature dependence in their hyperfine coupling constants (hfccs). The origin of this behavior has been only qualitatively interpreted as temperature-dependent positional change or migration of the alkali-metal cation to the oxygen atoms of the o-semiquinone radical. A quantitative discussion of such dynamic behavior has not been carried out to date. Recently, we synthesized and isolated corannulene (1)based stable neutral monoand diradical derivatives with bowl-shaped non-alternant p-conjugated systems. Their three-dimensional spin-delocalized nature and intraand intermolecular magnetic interactions were experimentally illustrated in terms of geometrical and topological aspects. These studies have inspired us to design a novel bowl-shaped radical anion system 2C based on corannulene with the o-

Preparation and magnetic properties of metal-complexes from N-t-butyl-N-oxidanyl-2-amino-(nitronyl nitroxide).

Metal complexation reactions of N-t-butyl-N-oxidanyl-2-amino(nitronyl nitroxide) diradical (1) with M(hfac)2 (M: Mn or Cu) were investigated. These reactions were found to be very sensitive to the type of metal ion employed. Complex [Mn(hfac)2·1], consisting of Mn(hfac)2 and diradical 1, was readily prepared by mixing the components. However, the reaction of Cu(hfac)2 with 1 or N-t-butyl-N-oxidanyl-2-amino(iminonitroxide) diradical (2) involved the reduction of the diradical to the N-t-butyl-N-oxidanide-2-amino(iminonitroxide) radical anion (3) and finally produced the polymer-chain complex [Cu2(hfac)2·32·Cu(hfac)2]n. The structures of these complexes were elucidated by X-ray analysis, and their magnetic properties were investigated in detail. The temperature dependence of χpT (χp: magnetic susceptibility) for [Mn(hfac)2·1] exhibited a strong antiferromagnetic interaction (H = -2JS1·S2, J/kB = -217 K) between the Mn(II) spin (S = 5/2) and the diradical 1 spin (S = 1). However, the χpT-T plots for [Cu2(hfac)2·32·Cu(hfac)2]n indicated the presence of several magnetic interactions: a large ferromagnetic interaction (J/kB = 510 K) between iminonitroxide 3 and the imino-coordinating Cu(II) atom, a moderately large ferromagnetic interaction (J/kB = 58 K) between the iminonitroxide and (iminonitroxide oxygen)-coordinating Cu(hfac)2, and a weak antiferromagnetic interaction (J/kB = -1.4 K) between the two Cu(hfac)-3 moieties within a Cu2O2 square.

Pulsed electron spin nutation spectroscopy of weakly exchange-coupled biradicals: a general theoretical approach and determination of the spin dipolar interaction

Weakly exchange-coupled biradicals have attracted much attention in terms of their DNP application in NMR spectroscopy for biological systems or the use of synthetic electron-spin qubits. Pulse-ESR based electron spin nutation (ESN) spectroscopy applied to biradicals is generally treated as transition moment spectroscopy from the theoretical side, illustrating that it is a powerful and facile tool to determine relatively short distances between weakly exchange-coupled electron spins. The nutation frequency as a function of the microwave irradiation strength ω(1) (angular frequency) for any cases of weakly exchange-coupled systems can be classified into three categories; D(12) (spin dipolar interaction)-driven, Δg-driven and ω(1)-driven nutation behaviour with the increasing strength of ω(1). For hetero-spin biradicals, Δg effects can be a dominating characteristic in the biradical nutation spectroscopy. Two-dimensional pulse-based electron spin nutation (2D-ESN) spectroscopy operating at the X-band can afford to determine small values of D(12) in weakly exchange-coupled biradicals in rigid glasses. The analytical expressions derived here for ω(1)-dependent nutation frequencies are based on only four electronic spin states relevant to the biradicals, while real biradical systems often have sizable hyperfine interactions. Thus, we have evaluated nuclear hyperfine effects on the nutation frequencies to check the validity of the present theoretical treatment. The experimental spin dipolar coupling of a typical TEMPO-based biradical 1, (2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2)]piperidin-N-oxyl-4-yl)(2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2),(15)N]piperidin-(15)N-oxyl-4-yl) terephthalate in a toluene glass, with a distance of 1.69 nm between the two spin sites is D(12) = -32 MHz (the effect of the exchange coupling J(12) is vanishing due to the homo-spin sites of 1, i.e.Δg = 0), while 0 < |J(12)|≦ 1.0 MHz as determined by simulating the random-orientation CW ESR spectra of 1. In addition, we have carried out Q-band pulsed ELDOR (ELectron-electron DOuble Resonance) experiments to confirm whether the obtained values for D(12) and J(12) are accurate. The distance is in a fuzzy region for the distance-measurements capability of the conventional, powerful ELDOR spectroscopy. The strong and weak points of the ESN spectroscopy with a single microwave frequency applicable to weakly exchange-coupled multi-electron systems are discussed in comparison with conventional ELDOR spectroscopy. The theoretical spin dipolar tensor and exchange interaction of the TEMPO biradical, as obtained by sophisticated quantum chemical calculations, agree with the experimental ones.