Laboratory for Physical Chemistry 2: Molecular Spin
Science

http://www.sci.osaka-cu.ac.jp/chem/phy2/phy2.html

Current Research and Principal Research Interests
Selected Publications

1. Current Research and Principal Research Interests
Major research interests in our group fall into over ten areas and categories of chemistry andmaterials science, centering on the advancement of molecular spin science and on the significant
contribution to the conceptual and material advance in organic molecule-based magnetism andmagnetics. A major goal of our study on molecular spin science is to develop spin-mediatedmolecular devices in terms of novel functionality concepts and materials challenge, stimulating
actual molecular designing and organic syntheses of component key-molecules. Both molecularspin science and organic molecule-based magnetics are underlain by high-spin chemistry andmaterial development in novel open-shell molecular systems and magnetic molecularassemblages. Molecular design and synthetic challenges for chemically stable and genuinely
organic open-shell systems have particularly been emphasized in our recent research efforts. Our
principal interests focus on not only the fundamental understanding of spin alignment in organic
high-spin systems and the establishment of conceptual advance in molecule-based magnetics,
but also search for novel quantum phenomena and molecular functionalities derived fromgenuinely organic open-shell molecular systems. A novel concept, “Molecular Spinics” termedby us includes redox-based spin electronics underlying molecular organic charge storage
devices. These new molecular quantum functionalities are based on quantum chemical
considerations and methodology developed in high-spin chemistry and genuinely organic
molecule-based magnetics. Our recent findings of redox-based spin diversity provide us with not
only a new field of chemistry and related molecular spin science, but also material andtechnological advance such as organic molecular batteries. The spin diversity originates in“molecular diversity” intrinsic to molecular systems, not appearing in atomic ones alone. In thiscontext, the spin diversity is a quantum aspect of molecular diversity. Our long-standing
expertise in these particular fields since 1970 has been utilized to search for such novel
molecular functionalities.
Our sixteen principal research interests are as follows:(1) Molecular spinics underlain by organic high-spin chemistry and organic molecule-basedmagnetics: Theory and Applications.
Our current interests include superparamagnetic nanochemistry and magnetic quantum-welleffects as well as molecular spin quantum tunneling which has been shown in the study ofpolyanionic C60 fullerene in the high-spin and low-spin states. The C60 polyanionic systems
with high molecular symmetry have shown dynamic Jahn-Teller assisted molecular hot-phononbottleneck phenomena, which is the first example of phonon bottleneck phenomenon for organic
systems. The findings of the dynamic Jahn-Teller effects have given for the first time anexperimental evidence for the occurrence of dynamic Jahn-Teller effects responsible for high-Tc
superconductivity in alkaline-doped C60 molecular crystalline systems, which has been
predicted by physicists from the theoretical side. Our current interests include also to find novel
quantum modes originating in semi-microscopic superlattices such as periodicallyfine-structured ferromagnetic thin films of one- or two-dimension (see Figure 1). We have forthe first time shown the occurrence of lateral “Walker modes” (spin-waves standing along they-direction) from the superlattices on a micron scale in terms of ferromagnetic resonancespectroscopy (see Figure 2).

Figure 1. 2D Superlattice composed of ferromagnetic thin films on a
micron scale used for ferromagnetic resonance spectroscopy; Thin film
width = 50 nm and W = S= 2 μm.

Figure 2. Observed ferromagnetic resonance spectra from the 1d superlatticeof n = 100 with B0 // y and theoretically calculated stick spectra for lateral
Walker mode spin waves and spin dipolar spin waves.

(2) Nonlinear oscillations of gigantic spin-magnetic moments in artificial superlattices on asemi-microscopic scale.

Nonlinear oscillation phenomena from the one- and two-dimensional superlattices withmicrowave field B1 parallel to B0 have been observed at certain conditions, illustrating thepossible device of self-oscillation in microwave frequency range. The two-dimensional tiled
superlattices show group-theoretical pseudo-degeneracy in a semi-microscopic scale.
(3) New trend in high spin chemistry: electronically ground and excited high-spin states from
π-conjugated oligocarbenes and oligonitrenes.
Oligocarbene-based high-spin chemistry has been a well established area in molecule-basedmagnetics. High spin chemistry has underlain molecule-based magnetism, bringing about
conceptual advances such as π-topologically controlled spin polarization (π-topology rule inspin alignment). A New trend in high spin chemistry includes detection and characterization of
excited states of open-shell oligocarbenes. Various excited states with different spin
multiplicities are located close to the high spin ground states, generating salient features forhigh-spin open-shell molecular systems. Their electronic spin structures are particular interestsand have drawn general attention from both theoretical and experimental sides. We have studied
absorption and emission spectra from typical triplet and quintet carbenes and have made efforts
to identify electronic transitions by invoking the latest and most reliable ab initio quantumchemical computations.
The new trend also includes advance in oligonitrene chemistry. Referred to the electronic andmolecular structures of high-spin oligonitrenes, documentation so far since 1967 has been
misleading and most of the reported fine-structure parameters have never reproduced thecorresponding observed fine-structure spectra in non-oriented media. We have solved thislong-standing issue from both theoretical and experimental sides, establishing molecular design
for stable oligonitrenes of desired fine-structure tensors.
(4) New π-topology-controlled high-spin hydrocarbons: development of polynuclear benzenoid
high-spin chemistry.
Besides well established π-topology rule, we have proposed new types of π-topologycontrolled molecular design for super high-spin and ferromagnetic hydrocarbons of one- or
two-dimension from theoretical side. One of such molecular designs is triangulene-based.
During the course of this project, we have synthesized, detected and characterized stabilized
triangulene (Clar’s hydrocarbon) in the triplet ground state, for the first time. The molecular
design has been based on new molecular diversity of hydrocarbons of π-conjugation. The
project has been run in collaboration with the group of Professors K. Nakasuji and Y. Morita,
Osaka University.
(5) Development of new methodology and experimental techniques in pulsed electrn spinresonance spectroscopy: Transition moment spectroscopy as a novel spectroscopy.
Our particular interests focus on establishment and a wide variety of applications of
two-dimensional (2D) electron spin transient nutation spectroscopy as new transition moment
spectroscopy (see Figures below for an echo-detected scheme and for a field-swept 2D
representation. We have already made quite a number of applications in high-spin chemistry,illustrating that the pulse-based nutation spectroscopy is facile and powerful in straightforwardly
identifying spin multiplicities as well as ESR transition assignments involved under study. The
ESR transition assignments include both fine-structure allowed and forbidden transitions in
non-oriented media and hyperfine allowed and forbidden ones in single crystals in terms ofcorresponding nutation frequencies appearing in the rotating frame of microwave irradiation.
Inversion recovery methods applied to the trianionic C60 fullerene systems have given
evidence for the occurrence of such quantum spin tunneling between the doublet-quartet states
for the trianionic case as is assisted by spin-vibronic dynamic Jahn-Teller interactions andhot-phonon bottleneck phenomena (see Figure 3 for the triplet-singlet resonant spin tunnelingoccurring in the dianionic C60 fullerene system). The tunneling frequencies and sizes ofresponsible nuclear displacements have quantum-mechanically been derived in terms ofdynamic treatments with nuclear kinetic energies. The results have given a rationale for theoccurrence of the dynamic Jahn-Teller mechanism in the high Tc superconducting states ofalkaline-doped C60 molecular crystals, which has been predicted by theoretical physicists.

(6) Parametric (parallel polarization) excitation spectroscopy: general theory and applications.
In high-spin chemistry in terms of spin identification, parametric excitation of microwave
irradiation gives ample information on fine-structure terms. We have frequently applied theparametric excitation spectroscopy to molecular magnetic systems which have large
fine-structure interactions, in some cases to high-spin systems characterized by non-vanishinglarge orbital angular momenta. The data derived from the parametric excitation spectroscopy
have been complementary to those acquired by highfield/highfrequency ESR spectroscopy insome cases. General exact analytical solutions for the motion of spin magnetization inparametric excitation spectroscopy have been obtained by invoking exponential operator
techniques, emphasizing that the general exact analytical solutions predict the occurrence ofmultiple-harmonic frequency oscillations in parametric excitation spectroscopy. General theory
for the motion of any spin magnetization in the presence of static and oscillating irradiation
fields of various types gives new aspects and physical pictures in magnetic resonancespectroscopy.

Figure 3. Spin relaxation curves for the annealed C602- with the triplet state
at 12.9K. The solid curve represents the theoretical curve derived from themodified Scott-Jeffries equation combined with a sine curve with thefrequency of 30 kHz.

(7) General theory of magnetic resonance spectroscopy.
Our current interests focus on the development of fine-structure spectral simulation methods
which execute facile and fast simulation processes. Fine-structure spectral simulations haveenjoyed “notorious drawbacks” for a long time. A remarkable advance in
highfield/highfrequncy ESR spectroscopy has decreased crucial needs for sophisticatedfine-structure spectral simulations, which gives straightforward transition assignments for manycases. Nevertheless, recently non-ESR-specialist chemists or materials scientists working ininterdisciplinary fields often need reliable X-band ESR fine-structure spectral simulations andmethodology to understand magnetic properties and electronic spin structures of a variety ofhigh-spin systems. We have appreciated the eigenfield approach introduced by Belford et al. in
1970’s. Owing to ultrafast computer facilities, sizable computations based on numerical matrix
diagonalization for the simulation seem feasible. Speaking exactly, this is still not the case forhigh-spin fine-structure chemistry. We have made efforts to develop much more reliable andfast-access approach termed “hybrid eigenfield approach” devoted to high-spin chemistry andhigh-spin ESR spectroscopy. Program softwares have been distributed on request for chemists
and materials scientists working in the fields of molecule-based magnetism and high spinchemistry.
(8) Paramagnetic metalloporphyrin chemistry related to biological implications: Jahn Tellerinteractions in low symmetry.
The overall goals of our current research programs are to elucidate electronic structures anddistorted molecular geometries of ferric iron porphryin in the sextet ground state andcobalt(II)porphyry in the low-spin doublet state. Both systems undergo sizable static Jahn-Teller
distortions at liquid helium temperatures. Single-crystal ESR and ENDOR spectroscopy has
been applied to identify distorted molecular structures and to elucidate peculiar electronic
structures. Concepts of nuclear spin degenerate state ENDOR have frequently used tounderstand complicated 14N-ENDOR spectra. It has shown for the first time that referred to theelectronic structure of fifth-ligand non-coordinated cobalt(II)porphyrin frequently applied
Magarvey’s model breaks down.
(9) Electron-nuclear multiple resonance in organic high-spin chemistry and paramagnetic metal
complexes.
(10) Crystal Engineering for purely organic high-spin molecular crystals.
Genuinely organic molecule-based ferrimagnetics is the focus of our current issues in thisparticular area, simply because genuinely organic ferrimagnets have not been documented yet.
Organic ferrimagnetics also gives new aspects in the research field of magnetism as well as
chemistry. A concept of “magnetic supramolecule” has been proposed in magnetic molecular
crystals and molecular crystal engineering.
(11) VB theory for charge fluctuation vs. spin polarization in high-spin polyanionic andpolycationic systems.
(12) Chememometric 2D electron spin resonance spectroscopy.
(13) Molecularinformatics and chemoinformatics.
(14) Chemometrics for environmental radiation damages.
These projects (12)-(14) have recently launched for biologically important metal complexes
and medical applications, and several issues are underway for generalization. The issues understudy are categorized into generalized two-dimensional correlation spectroscopy handlingexperimental data in a sizable scale.
(15) Photo-storage molecular materials luminescence spectroscopy and molecular batteries.
Our group strives to develop molecular spin science, understanding electronic structures andmagnetic properties of novel high-spin molecular systems underlying molecule-based magnetic
materials. On the basis of the electronic structures we have developed the theory of molecular
design of molecule-based high-spin systems. Molecular systems applied are in a wide range
from organic high-spin systems to inorganic polynuclear complexes. The organic systems
include polyradicals, high-spin oligocarbenes and oligonitrenes, and in addition, the polyionicstates of the organic molecules. All compounds possess a high-spin ground or thermallyaccessible excited states. The inorganic systems include not only magnetically coupledtransition metal systems but also rare earth metals. One of the rare earth metal systems which weare currently interested in is europium(II)-doped aluminates which are remarkably long-lasting
phosphors. The aluminate is free of hazardous and radioactive substances, and has been
attracting interest because of its potential for a variety of applications. In order to elucidate thelong-lasting mechanisms, we have applied highfield/highfrequency ESR spectroscopy to thesystems in collaboration with Professor T. Kato, IMS and with Professor W. Lubitz, TU in
Berlin.
(16) Quantum chemistry of fine-structure interactions in high-spin systems with high molecularsymmetry.
Polyionic states of highly symmetric molecules have been attracting interest with respect tosymmetry-lowering distortions by the Jahn-Teller effect in degenerate electronic states such aspolyanionic decacyclene. Preference for the high-spin ground states resulting from the robust
dynamic spin polarization has been a long-standing issue for trianionic decacyclene. In terms ofspin correlation in the open-shell systems, our current research efforts are directed toward
quantum chemical calculations of the fine-structure terms in highly symmetric πconjugation
systems. Recently, we have detected for the first time a Clar’s hydrocarbon in the triplet groundstate. The Clar’s hydrocarbnon is neutral and triangular molecule with a highly delocalized
π-system.
Referred to highly symmetric molecules of π-spin delocalization, we
have reported high-spin states of polyanionic C60 fullerene anddecacyclene prepared by chemical reduction with alkali metals. As
described above, we have found the anomalous spin relaxation due tophonon bottleneck and quantum-mechanical tunneling phenomena in
the polyanionic C60 fullerene. In the case of the highly symmetricmolecule in the high spin state, the pseudo Jahn-Teller interaction is
responsible for the occurrence of the quantum tunneling phenomena.
Noticeably, the Jahn-Teller assisted quantum spin tunneling observedin polyanionic C60 fullerene supports a theoretical model proposed for high-temperature
superconductivity in fullerides with alkali metals. On the other hand, decacyclene withthree-fold symmetry has two degenerate LUMOs and a pseudo-degenerate MO above the
LUMOs in the neutral molecule. It has been well known that the trianionic state of decacyclene
is spin-doublet in the ground state. Theoretical calculations considering configuration interaction
also supported the doublet ground state for the trianionic state. Nevertheless, detection of thequartet state has been a long-standing issue because knowledge of this state is important forunderstanding of the Jahn-Teller effect in the high-spin state. On the contrary to the
documentation, we have recently detected the quartet state using fine-structure ESR
spectroscopy for random orientation. Our hybrid eigenfield approach has successfully
reproduced the observed spectra with all the forbidden transitions. It is concluded that thetrianionic state of decacyclene is in the quartet ground state, contrary to the previously
documented results, indicating that highly sophisticated quantum chemical calculations
incorporating vibronic and spin-orbit interactions are required.
Both polyanionic C60 fullerene and decacyclene possess two or three delocalized π-spins in thehigh-spin states. Spin-spin interaction in the three-spin system includes a fundamental issue forestablishing the ground-state electronic structure of the delocalized high-spin system. The
spin-spin interaction has been understood based on two-body interaction. Recently, we havenoticed that three-body interactions are essential for the understanding of spin-spin interactionsin the three spin systems. This issue has been overlooked for a long time even in high spinchemistry. Our findings contribute to the understanding and theoretical considerations of thespin-spin interaction in terms of the three-body quantum-mechanical problem. Quantum
chemical approach to fine-structure terms in terms of spin pair functions is underway.
2. Selected Publications
1. “Detection of an aromatic hydrocarbon in its septet electronic ground state by electron spinresonance”, T. Takui, K. Itoh, Chem. Phys. Lett., 19, pp. 120-124 (1973).
2. “General description of multiple-modulation effects and sideband production in magnetic
resonance”, H. Sakamoto, T. Takui, K. Itoh, Can. J. Chem., 66, pp. 3077-3082 (1988).
3. “Design, preparation, and electron spin resonance detection of a ground-state undecet (S = 5)hydrocarbon”, I. Fujita, Y. Teki, T. Takui, T. Kinoshita, K. Itoh, J. Am. Chem. Soc., 112, pp.
4074-4075 (1990).
4. “Novel organic ions of high-spin states. 2. Determination of the spin multiplicity of theground state and 1H-ENDOR study of the monoanion of m-phenylenebis(phenylmethylene)”,M. Matsushita, T. Nakamura, T. Momose, T. Shida, Y. Teki, T. Takui, T. Kinoshita, K. Itoh, J.
Am. Chem. Soc., 114, pp. 7470-7475 (1992).
5. “Polycationic high-spin states of one- and two-dimensional (diarylamino)benzenes,
prototypical model units for purely organic ferromagnetic metals as studied by pulsed
ESR/electron spin transient nutation spectroscopy”, K. Sato, M. Yano, M. Furuichi, D. Shiomi,
T. Takui, K. Abe, K. Itoh, A. Higuchi, K. Katsuma, Y. Shirota, J. Am. Chem. Soc., 119, pp.
6607-6613 (1997).
6. “Persistent high-spin polycarbene. Generation of polybrominated 1,3,5-tris-[2[4-(phenylcarbeno)phenyl]thynyl]benzene (S = 3) and spin identification by two-dimensional
electron spin transient nutation spectroscopy”, H. Tomioka, M. Hattori, K. Hirai, K. Sato, D.
Shiomi, T. Takui, K. Itoh, J. Am. Chem. Soc., 120, pp. 1106-1107 (1998).
7. “Electronic quartet and triplet states of polyanionic C-60 fullerene and their anomalous spin
relaxation as studied by cw-ESR/2D-Electron spin transient nutation spectroscopy”, M. C. B. L.
Shohoji, M. L. T. M. B. Franco, M. C. R. L. R. Lazana, S. Nakazawa, K. Sato, D. Shiomi, T.
Takui, J. Am. Chem. Soc., 122, pp. 2962-2963 (2000).
8. “Evidence for the breakdown of simple classical pictures of organic molecule-based
ferrimagnetics: Low-temperature crystal structure and single-crystal ESR studies of an organic
heterospin system”, M. Nishizawa, D. Shiomi, K. Sato, T. Takui, K. Itoh, H. Sawa, R. Kato, H.
Sakurai, A. Izuoka, T. Sugawara, J. Phys. Chem. B, 104, pp. 503-509 (2000).
9. “Single-component molecule-based ferrimagnetics”, D. Shiomi, T. Kanaya, K. Sato, M. Mito,
K. Takeda, T. Takui, J. Am. Chem. Soc., 123, pp. 11823-11824 (2001).

10. “The first detection of a Clar’s hydrocarbon, 2,6,10-tri-tert-butyltriangulene: A ground-state
triplet of non-Kekule polynuclear benzenoid hydrocarbon”, J. Inoue, K. Fukui, T. Kubo, S.
Nakazawa, K. Sato, D. Shiomi, Y. Morita, K. Yamamoto, T. Takui, K. Nakasuji, J. Am. Chem.
Soc., 123, pp. 12702-12703 (2001).