Kyushu University Academic Staff Educational and Research Activities Database
List of Papers
Haruyuki Nakano Last modified date:2018.06.27

Professor / interdisciplinary chemistry / Department of Chemistry / Faculty of Sciences


Papers
1. Satoshi Omomo, Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines
A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers, Angewandte Chemie - International Edition, 10.1002/anie.201800471, 57, 14, 3797-3800, 2018.03, We have established a convenient method for the base-promoted direct amination of β-unsubstituted 5,15-diazaporphyrins (DAPs) with secondary and primary amines to produce 3,7,13,17-tetraamino- and 3-amino-DAPs, respectively, regioselectively. The amino groups attached at the periphery cause significant red shifts of the absorption bands as a result of their perturbation of the HOMO and/or LUMO in the DAP π-system. The palladium complex of a 3,7,13,17-tetrakis(diphenylamino)-DAP generated singlet oxygen in high yield under irradiation with near-infrared light..
2. Keisuke Sudoh, Takuroh Hatakeyama, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano, Redox switchable 19π and 18π 5,10,20-triaryl-5,15-diazaporphyrinoid–nickel(II) complexes, Journal of Porphyrins and Phthalocyanines, 10.1142/S1088424618500529, 1-10, 2018.01, The synthesis and optical, electrochemical, and magnetic properties of nickel(II) complexes of 5,10,20-triaryl-5,15-diazaporphyrin (TriADAP) are reported. Metal-templated cyclization of unsymmetrically substituted nickel(II)–bis(1-amino-9-chloro-5-mesityldipyrrin; mesityl = 2,4,6-trimethylphenyl) complexes afforded the corresponding TriADAPs or 5-aryl-15-benzyl-10,20-dimesityl-5,15-diazaporphyrin, depending on the combination of base and solvent. The latter macrocycle was converted to TriADAP by deprotection of the (Formula presented.)-benzyl group through Pd/C-promoted hydrogenation. TriADAPs were isolated in both 18(Formula presented.) (cation) and 19(Formula presented.) (neutral) forms. The interconversion between these two oxidation states resulted in a distinct change in the optical properties of the DAP (Formula presented.)-system. NMR spectroscopy of the 18(Formula presented.) TriADAP cations showed that they had aromatic character, whereas EPR spectroscopy of the 19(Formula presented.) TriADAP showed a highly delocalized electron spin of the (Formula presented.)-radical. The para substituents of the (Formula presented.)-aryl groups of TriADAPs had a small but distinct impact on their HOMO and LUMO energies. The change in the net charge of one electron was directly reflected in the redox properties of the DAP ring; TriADAP was more easily reduced and less easily oxidized than DAP. The difference in the net charge was also reflected by the shielding of the pyrrolic β-protons observed in the (Formula presented.)H NMR spectra. The present results confirm that TriADAP is a highly promising framework for constructing a new class of azaporphyrin-based materials with 18(Formula presented.)–19(Formula presented.) redox-switchable optical and magnetic properties..
3. Keisuke Sudoh, Takaharu Satoh, Toru Amaya, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20π, 19π, and 18π 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids, Chemistry - A European Journal, 10.1002/chem.201703664, 23, 64, 16364-16373, 2017.11, In spite of significant advances in redox-active porphyrin-based materials and catalysts, little attention has been paid to 20π and 19π porphyrins because of their instability in air. Here we report the meso-modification of 5,10,15,20-tetraarylporphyrin with two nitrogen atoms, which led to redox-switchable 20π, 19π, and 18π 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs). Three kinds of metal(II) complexes and free bases of TADAP were prepared by the metal-templated annulation of the corresponding metal-bis(dipyrrin) complexes. The inductive and resonance effects of the meso-nitrogen atoms on the aromatic, optical, electrochemical, and magnetic properties of the entire TADAP π-systems were assessed by using various spectroscopic measurements and density functional theory calculations. The aromaticity and π–π* electronic transition energies of the TADAPs varied considerably, and were shown to be dependent on the oxidation states of the π-systems. In contrast to the isoelectronic 5,10,15,20-tetraarylporphyrin derivatives, the 20π and 19π TADAPs were chemically stable under air. In particular, the 19π TADAP radical cations were extremely stable towards dioxygen, moisture, and silica gel. This reflected the low-lying singly occupied molecular orbitals of their π-systems and the efficient delocalization of their unshared electron spin. The capability of MgTADAP to catalyze aerobic biaryl formation from aryl Grignard reagents was demonstrated, which presumably involved a 19π/20π redox cycle..
4. Yuichi Tanaka, Yukio Kawashima, Norio Yoshida, Haruyuki Nakano, Solvatochromism and preferential solvation of Brooker's merocyanine in water–methanol mixtures, Journal of Computational Chemistry, 10.1002/jcc.24902, 38, 28, 2411-2419, 2017.10, The excitation energy of Brooker's merocyanine in water–methanol mixtures shows nonlinear behavior with respect to the mole fraction of methanol, and it was suggested that this behavior is related to preferential solvation by methanol. We investigated the origin of this behavior and its relation to preferential solvation using the three-dimensional reference interaction site model self-consistent field method and time-dependent density functional theory. The calculated excitation energies were in good agreement with the experimental behavior. Analysis of the coordination numbers revealed preferential solvation by methanol. The free energy component analysis implied that solvent reorganization and solvation entropy drive the preferential solvation by methanol, while the direct solute–solvent interaction promotes solvation by water. The difference in the preferential solvation effect on the ground and excited states causes the nonlinear excitation energy shift..
5. Satoshi Omomo, Yukihiro Tsuji, Kenichi Sugiura, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori, Yoshihiro Matano, Unsymmetrically Substituted Donor–π–Acceptor-Type 5,15-Diazaporphyrin Sensitizers
Synthesis, Optical and Photovoltaic Properties, ChemPlusChem, 10.1002/cplu.201700051, 82, 5, 695-704, 2017.05, The first examples of unsymmetrical β-substituted donor–π–acceptor (D–π–A)-type 5,15-diazaporphyrin (DAP) sensitizers with both p-aminophenyl and p-carboxyphenyl groups at their peripheral 3-, 7-, 13-, and/or 17-positions have been synthesized for use in dye-sensitized solar cells (DSSCs). UV/Vis absorption and emission spectroscopy, electrochemical measurements, and DFT calculations revealed that these D–π–A dyes exhibit high light-harvesting properties over the whole visible range because of the intrinsic charge-transfer character of their electronic transitions. The cell performances of TiO2-based DSSCs fabricated with the newly prepared DAP derivatives were evaluated under standard AM1.5 conditions. Among the four dyes examined, 13,17-bis(p-carboxyphenyl)-3,7-bis[p-(N,N-dimethylamino)phenyl]-DAP showed the highest power conversion efficiency (2.0 %), which was 20 times larger than that obtained with 3-(p-carboxyphenyl)-DAP. These results show that the DAP chromophore could be used as the electron-accepting π unit in various types of functional dyes..
6. Masahiro Kawamata, Takuma Sugai, Mao Minoura, Yasuhisa Maruyama, Ko Furukawa, Cole Holstrom, Victor N. Nemykin, Haruyuki Nakano, Yoshihiro Matano, Nitrogen-Bridged Metallodiazaporphyrin Dimers
Synergistic Effects of Nitrogen Bridges and meso-Nitrogen Atoms on Structure and Properties, Chemistry - An Asian Journal, 10.1002/asia.201700204, 12, 7, 816-821, 2017.04, NH-bridged and pyrazine-fused metallodiazaporphyrin dimers have been prepared from nickel(II) and copper(II) complexes of 3-amino-5,15-diazaporphyrin by Pd-catalyzed C−N cross-coupling and oxidative dimerization reactions, respectively. The synergistic effects of the nitrogen bridges and meso-nitrogen atoms play major roles in enhancing the light-harvesting properties and delocalization of an electron spin over the entire π-skeletons of the metallodiazaporphyrin dimers..
7. Nirun Ruankaew, Norio Yoshida, Yoshihiro Watanabe, Haruyuki Nakano, Saree Phongphanphanee, Size-dependent adsorption sites in a Prussian blue nanoparticle
A 3D-RISM study, Chemical Physics Letters, 10.1016/j.cplett.2017.06.053, 684, 117-125, 2017, The specific adsorption of alkali ions, Li+, Na+, K+, and Cs+, in electrolyte solutions on Prussian blue (PB) is investigated by using the three-dimensional (3D) reference interaction site-model (RISM) theory. The results from 3D-RISM show dramatically different adsorption sites between large ions (K+ and Cs+) and small ions (Li+ and Na+). The small ions are adsorbed at the channel entrance sites without the water–ion exchange mechanism. In contrast, the large ions are adsorbed in PB by the water–ion exchange mechanism, and the adsorption site of large ions is located at the center of the cage or at the interstitial site..
8. Shoichi Tanimoto, Masahiro Higashi, Norio Yoshida, Haruyuki Nakano, The ion dependence of carbohydrate binding of CBM36
An MD and 3D-RISM study, Journal of Physics Condensed Matter, 10.1088/0953-8984/28/34/344005, 28, 34, 2016.07, The molecular recognition process of the carbohydrate-binding module family 36 (CBM36) was examined theoretically. The mechanism of xylan binding by CBM36 and the role of Ca2+ were investigated by the combined use of molecular dynamics simulations and the 3D reference interaction site model method. The CBM36 showed affinity for xylan after Ca2+ binding, but not after Mg2+ binding. Free-energy component analysis of the xylan-binding process revealed that the major factor for xylan-binding affinity is the electrostatic interaction between the Ca2+ and the hydroxyl oxygens of xylan. The van der Waals interaction between the hydrophobic side chain of CBM36 and the glucopyranose ring of xylan also contributes to the stabilization of the xylan-binding state. Dehydration on the formation of the complex has the opposite effect on these interactions. The affinity of CBM36 for xylan results from a balance of the interactions between the binding ion and solvents, hydrophilic residues around xylan, and the hydroxyl oxygens of xylan. When CBM binds Ca2+, these interactions are well balanced; in contrast, when CBM binds Mg2+, the dehydration penalty is excessively large..
9. Yuki Seno, Norio Yoshida, Haruyuki Nakano, Theoretical analysis of complex formation of p-carboxybenzeneboronic acid with a monosaccharide, Journal of Molecular Liquids, 10.1016/j.molliq.2015.12.063, 217, 93-98, 2016.05, Changes in the acid dissociation constant, pKa, of p-carboxybenzeneboronic acid (PCBA) upon complex formation with monosaccharide are considered by using the three-dimensional reference interaction site model self-consistent field theory. The pKa of PCBA is lowered through complex formation, which is consistent with experimental observations. Free energy component analysis of the dissociation reaction was performed to investigate the details of the contribution to the pKa shift. The magnitudes of the changes in both the electronic energy and the solvation free energy were smaller for the PCBA-complex than for PCBA. These smaller changes can be attributed to the delocalization of the excess charge and to a reduction of the solvent-accessible area near the boric acid group because of the steric bulk of the monosaccharide..
10. Takaharu Satoh, Mao Minoura, Haruyuki Nakano, Ko Furukawa, Yoshihiro Matano, Redox-switchable 20π-, 19π-, and 18π-electron 5,10,15,20-tetraaryl-5,15-diazaporphyrinoid nickel(II) complexes, Angewandte Chemie - International Edition, 10.1002/anie.201510734, 55, 6, 2235-2238, 2016.02, The first examples of air-stable 20π-electron 5,10,15,20-tetraaryl-5,15-diaza-5,15-dihydroporphyrins, their 18π-electron dications, and the 19π-electron radical cation were prepared through metal-templated annulation of nickel(II) bis(5-arylamino-3-chloro-8-mesityldipyrrin) complexes followed by oxidation. The neutral 20π-electron derivatives are antiaromatic and the cationic 18π-electron derivatives are aromatic in terms of the magnetic criterion of aromaticity. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins. N makes all the difference: Redox-switchable 20π-, 19π-, and 18π-electron 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids are prepared through metal-templated annulation of NiII bis(dipyrrin) complexes followed by oxidation. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins..
11. Yuichi Tanaka, Norio Yoshida, Haruyuki Nakano, Three-dimensional reference interaction site model self-consistent field analysis of solvent and substituent effects on the absorption spectra of Brooker's merocyanine, Journal of Computational Chemistry, 10.1002/jcc.23980, 36, 22, 1655-1663, 2015.08, Solvent and substituent effects on the absorption spectra of Brooker's merocyanine (BM) are investigated using the three-dimensional reference interaction site model self-consistent field method and time-dependent density functional theory. The π-π∗ excitation energies are computed for BM and its derivative 2,6-di-tert-butyl (di-t-Bu) BM. The behaviors of the computed excitation energies with increasing solvent polarity are in good agreement with those of the corresponding experimental measurements. In addition, analysis of the solute-solvent interaction energies and spatial distribution functions reveals that the effects of the solvent on the absorption spectra are reduced by the steric hindrance of the t-Bu groups. Furthermore, from the difference in the solute-solvent interaction energies of BM and di-t-Bu BM, it is shown that the effect of the t-Bu substituents on the absorption spectrum is greater in high-polarity solvents..
12. Satoshi Omomo, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano, Comparison of electronic effects of β-Aryl substituents on optical and electrochemical properties of 5,15-diazaporphyrin φ-systems, Journal of Porphyrins and Phthalocyanines, 10.1142/S1088424615500509, 19, 6, 775-785, 2015.06, The syntheses and optical/electrochemical properties of 3-Aryl-10,20-dimesityl-5,15-diazaporphyrin-metal complexes (MDAPs; mesityl = 2,4,6-trimethylphenyl; M = Ni, Zn) are reported. Treatment of 3-bromo-MDAPs with arylboronic acids in the presence of a Pd catalyst and a bulky phosphine ligand in a dioxane-water mixed solvent afforded the corresponding 3-Aryl-MDAPs in moderate to good yields. X-ray crystallographic analysis of p-EtO2CC6H4-NiDAP showed that the β-Aryl group was tilted toward the NiDAP ring, with a dihedral angle of 21.7°. In the UV-visible absorption spectra, all the Ar-MDAPs showed intense Q-bands attributable to HOMO-to-LUMO transitions. The para substituents were found to influence the HOMO energies, which eventually resulted in fine tuning of the HOMO-LUMO gaps of the diazaporphyrin chromophores. It is worth noting that the p-Ph 2NC6H4-ZnDAP showed broad absorption and emission bands in the visible-near-infrared regions. The large Stokes shifts and their linear solvation energy relationships vs. orientation polarizability show that this Ph 2N-substituted derivative has intrinsically high charge transfer from the triphenylamine (donor) to the ZnDAP (acceptor) unit. These experimental observations were supported by theoretical calculations for model Ar-ZnDAP compounds. These results confirm that the introduction of a highly electron-donating aryl group at the peripheral β-carbon is a promising strategy for enhancing the light-harvesting and light-emitting abilities of diazaporphyrin-based φ-systems in the visible-near-infrared regions..
13. Fawzi Abou-Chahine, Daisuke Fujii, Hiroshi Imahori, Haruyuki Nakano, Nikolai V. Tkachenko, Yoshihiro Matano, Helge Lemmetyinen, Synthesis and Photophysical Properties of Two Diazaporphyrin-Porphyrin Hetero Dimers in Polar and Nonpolar Solutions, Journal of Physical Chemistry B Materials, 10.1021/jp510903a, 119, 24, 7328-7337, 2015.06, Two diazaporphyrin (DAP)-porphyrin hetero dimers, in β-meso and β-β configurations, were prepared to study their photoinduced intramolecular electron transfer properties. The two meso nitrogen atoms in the porphyrin ring of DAP change its redox potential, making DAP more easily reduced, compared to its porphyrin counterpart. A charge-transfer from porphyrin to DAP in both hetero dimers was verified by versatile optical spectroscopic methods. The steady-state fluorescence spectra indicated an efficient intramolecular exciplex formation for both dimers. For the β-meso dimer, ultrafast time-resolved spectroscopic methods revealed the subpicosecond formation of two types of primary short-living (1-18 ps) intramolecular exciplexes, which relaxed in toluene to form a long-living final exciplex (1.4 ns) followed by a longer-living charge transfer complex (>5 ns). However, in benzonitrile, the lifetime of the final exciplex was longer (660 ps) as was that of the charge transfer complex (180 ps). The β-β analogue formed similar short-living exciplexes in both solvents, but the final exciplex and the charge transfer state had significantly shorter lifetimes. The electrochemical redox potential measurements and density functional theory calculations supported the proposed mechanism..
14. Yukako Kasai, Norio Yoshida, Haruyuki Nakano, Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture, Journal of Chemical Physics, 10.1063/1.4921432, 142, 20, 2015.05, The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol-1. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol-1. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form..
15. Tatsuya Aotake, Mitsuharu Suzuki, Naoki Aratani, Junpei Yuasa, Daiki Kuzuhara, Hironobu Hayashi, Haruyuki Nakano, Tsuyoshi Kawai, Jishan Wu, Hiroko Yamada, 9,9′-Anthryl-anthroxyl radicals
Strategic stabilization of highly reactive phenoxyl radicals, Chemical Communications, 10.1039/c4cc10104a, 51, 31, 6734-6737, 2015.04, Stable 9,9′-anthryl-anthroxyl radicals were synthesized and isolated, and the structures were fully characterized by single crystal X-ray diffraction analysis and ESR measurement. The resonance structure and steric protection of the peripheral positions and the most reactive 9-position of anthracene prolong the half-life of the radical in solution to 11 days. This journal is.
16. Tatsuya Aotake, Mitsuharu Suzuki, Naoki Aratani, Junpei Yuasa, Daiki Kuzuhara, Hironobu Hayashi, Haruyuki Nakano, Tsuyoshi Kawai, Jishan Wu, Hiroko Yamada, Erratum
9,9′-Anthryl-anthroxyl radicals: Strategic stabilization of highly reactive phenoxyl radicals (Chemical Communications (2015)), Chemical Communications, 10.1039/c5cc90112j, 51, 24, 2015.01.
17. Satoshi Omomo, Yasuhisa Maruyama, Ko Furukawa, Taniyuki Furuyama, Haruyuki Nakano, Nagao Kobayashi, Yoshihiro Matano, Optical, electrochemical, and magnetic properties of pyrrole- And thiophene-bridged 5,15-diazaporphyrin dimers, Chemistry - A European Journal, 10.1002/chem.201405482, 21, 5, 2003-2010, 2015.01, The first examples of pyrrole- and thiophenebridged 5,15-diazaporphyrin (DAP) dimers are prepared through Stille coupling reactions of nickel(II) and copper(II) complexes of 3-bromo-10,20-dimesityl-5,15-diazaporphyrin (mesityl = 2,4,6-trimethylphenyl) with the respective 2,5-bis-(tributylstannyl)heteroles. The effects of the heterole spacers and meso nitrogen atoms on the optical, electrochemical, and magnetic properties of the DAP dimers are investigated by UV/Vis absorption spectroscopy, density functional theory calculations, magnetic circular dichroism spectroscopy, cyclic voltammetry, and EPR spectroscopy. The heterole spacers are found to have a significant impact on the electronic transitions over the entire p-system. In particular, the pyrrolebridged DAP dimers exhibit high light-harvesting potential in the low-energy visible/near-infrared region owing to the intrinsic charge-transfer character of the lowest excitation..
18. Yoshihiro Matano, Yukiko Hayashi, Haruyuki Nakano, Hiroshi Imahori, N,S,P-hybrid donor-π-acceptor organic dyes for dye-sensitized solar cell
Synthesis, optical properties, and photovoltaic performances, Heteroatom Chemistry, 10.1002/hc.21188, 25, 6, 533-547, 2014.06, New donor-π-acceptor organic (D-π-A) dyes composed of triarylamine, oligothiophene, and phosphole subunits were prepared, and their optical and photovoltaic properties were investigated. The regioselective α-lithiation of the thiophene ring of 2-(thiophen-2-yl)phospholes bearing an ester group, followed by treatment with tributyltin chloride afforded 2-(5-(tributylstannyl)thiophen-2-yl)phosphole derivatives, which underwent Stille coupling with 5′-(p-(diarylamino)phenyl)-5-bromo-2,2′-bithiophene to give triarylamine-terthiophene-phosphole hybrid π systems bearing the terminal ester group. The alkaline hydrolysis of the ester group yielded the target dyes, bearing the carboxylic acid anchoring group. The UV-vis absorption spectra of the new N,S,P-hybrid dyes displayed broad and intense π-π∗ transitions with two absorptionmaxima in the visible region. Density functional theory (DFT) calculations of two dye models revealed that each highest occupied molecular orbital (HOMO) resides on the triarylamine-oligothiophene π network, whereas each lowest unoccupied molecular orbital (LUMO) is basically located on the phosphole subunit. In addition, the time-dependent DFT calculations of the models showed that the lowest energy bands of these hybrid dyes are mainly consisted of the HOMO-to-LUMO+1 and HOMO-to-LUMO transitions with the large intramolecular charge-transfer character. The N,S,P-hybrid-dye-sensitized TiO2 cells exhibitedmoderate power conversion efficiencies of up to 5.6%. The present findings corroborate the potential utility of the phosphole skeletons as the acceptor components in the D-π-A sensitizers..
19. Yoshihiro Matano, Daisuke Fujii, Tarou Shibano, Ko Furukawa, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori, Covalently linked 5,15-diazaporphyrin dimers
Promising scaffolds for a highly conjugated azaporphyrin π system, Chemistry - A European Journal, 10.1002/chem.201304626, 20, 12, 3342-3349, 2014.03, The first examples of β-β directly linked, acetylene-bridged, and butadiyne-bridged 5,15-diazaporphyrin dimers have been prepared by palladium-catalyzed coupling reactions of nickel(II) and copper(II) complexes of 3-bromo-10,20-dimesityl-5,15-diazaporphyrin (mesityl=2,4,6-trimethylphenyl). The effects of the linking modes and meso-nitrogen atoms on the structural, optical, electrochemical, and magnetic properties of the distributed π systems were investigated by using X-ray crystallography, UV/Vis absorption spectroscopy, DFT calculations, cyclic voltammetry, and ESR spectroscopy. Both the electronic and steric effects of the meso-nitrogen atoms play an important role in the highly coplanar geometry of the directly linked dimers. The direct β-β linkage produces enhanced π conjugation and electron-spin coupling between the two diazaporphyrin units..
20. Mitsuharu Suzuki, Tatsuya Aotake, Yuji Yamaguchi, Nao Noguchi, Haruyuki Nakano, Ken ichi Nakayama, Hiroko Yamada, Synthesis and photoreactivity of α-diketone-type precursors of acenes and their use in organic-device fabrication, Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 10.1016/j.jphotochemrev.2013.10.003, 18, 50-70, 2014.03, Acenes are highly promising p-type organic semiconductors, and have been the subject of intense studies. However, acenes are often low in solubility and stability, which poses major obstacles in the synthesis and processing of this class of compounds. In order to overcome the problem, a series of α-diketone-type acene precursors have been developed. These precursors are generally more soluble and stable than the corresponding acene compounds, and their quantitative conversion can be achieved simply by photoirradiation both in solution and in the solid state. Further, the irreversible photoinduced removal of the α-diketone unit can be used to alter the optoelectronic properties of fluorophores. This review overviews the synthesis and photochemical properties of α-diketone-type acene precursors, as well as their use as intermediates in preparation of large acenes or highly functionalized acene derivatives. Computational studies on the mechanism of α-diketone photolysis and the use of α-diketone derivatives in fabrication of organic devices are also summarized in this review..
21. Y. Kawashima, S. Yamamoto, T. Sakata, H. Nakano, K. NIshiyama, R. Akiyama, Solvent Effect on the Fluorescence Spectra of Coumarin 120 in Water: A Combined Quantum Mechanical and Molecular Mechanical Study, J. Phys. Soc. Jpn., 81, SA024/1-8, 2013.11.
22. Y. Tanaka, N. Yoshida, H. Nakano, Solvent effect on excited states of merocyanines: A theoretical study using the RISM-SCF method, Chem. Phys. Lett., 583, 69-73, 2013.09.
23. S. Fujishige, Y. Kawashima, N. Yoshida, H. Nakano, Three-dimensional Reference Interaction Site Model Self-consistent Field Study of the Solvation and Electronic Structures of [Cr(H2O)6]3+ in Aqueous Solution, J. Phys. Chem. A, 117, 8314-8322, 2013.08.
24. Y. Matano, T. Shibano, H. Nakano, Y. Kimura, H. Imahori, Free Base and Metal Complexes of 5,15-Diaza-10,20-dimesitylporphyrins: Synthesis, Structures, Optical and Electrochemical Properties, and Aromaticities, Inorg. Chem., 51, 12879-12890, 2012.11.
25. T. Okujima, T. Kikkawa, H. Nakano, H. Kubota, N. Fukugami, N. Ono, H. Yamada, H. Uno, Retro-Diels-Alder Approach to the Synthesis of pi-Expanded Azuliporphyrins and Their Porphyrinoid Aromaticity, Chem. Eur. J., 18, 12854-12863, 2012.08.
26. Y. Matano, T. Shibano, H. Nakano, H. Imahori, Nickel(II) and Copper(II) Complexes of beta-Unsubstituted 5,15-Diazaporphyrins and Pyridazine-Fused Diazacorrinoids: Metal-Template Syntheses and Peripheral Functionalizations, Chem. Eur. J., 18, 6208-6216, 2012.03.
27. Y. Kawashima, H. Nakano, J. Jung, S. Ten-no, A combined quantum mechanical and molecular mechanical method using modified generalized hybrid orbitals: implementation for electronic excited states, Phys. Chem. Chem. Phys., 11, 11731-11738, 2011.05.
28. R. Ebisuzaki, Y. Watanabe, Y. Kawashima, and H. Nakano, Parallel implementation of the four-commponent relativistic quasidegenerate perturbation theory with general multiconfigurational reference functions, J. Chem. Theory Comp., 10.1021/ct2000205, 7, 998-1005, 2011.04.
29. S. Suzuki, R. Ebisuzaki, Y. Kawashima, Y. Watanabe, H. Nakano, Efficient and Accurate Approximation to Relativistic Multireference Perturbation Theory, Kyushu University Global-COE program, Science for Future Molecular Systems, Journal, 5, 41-43, 2011.04.
30. H. Sato, H. Uno, and H. Nakano, Identification of geometrical isomers using vibrational circular dichroism spectroscopy: a series of mixed-ligand complexes of diamagnetic Co(III) ions, Dalton Trans., 10.1039/C0DT01342K, 40, 1332-1337, 2011.02.
31. T. Sakata, Y. Kawashima, and H. Nakano, Solvent effect on the absorption spectra of coumarin 120 in water: A combined quantum mechanical and molecular mechanical study, J. Chem. Phys., 10.1063/1.3506616, 134, 014501/1-11, 2011.01.
32. T. Sakata, Y. Kawashima, and H. Nakano, Low-Lying Excited States of C120 and C151: A Multireference Perturbation Theory Study, J. Phys. Chem. A, 10.1021/jp1019872, 114, 12363-12368, 2010.12.
33. Y. Watanabe, H. Nakano, and H. Tatewaki, Effect of removing the no-virtual pair approximation on the correlation energy of the He isoelectronic sequence. II. Point nuclear charge model, J. Chem. Phys., 132, 12, 124105 , 2010.03.
34. H. Moriyama, Y. Watanabe, H. Nakano, S. Yamamoto, and H. Tatewaki, Electronic structure of LaO based on frozen-core four-component relativistic multiconfigurational quasidegenerate perturbation theory, J. Chem. Phys. , 132, 12, 124310, 2010.03.
35. T. Nakabuchi, M. Nakashima, S. Fujishige, H. Nakano, Y. Matano, and H. Imahori, Synthesis and Reactions of Phosphaporphyrins: Reconstruction of pi-Skeleton Triggered by Oxygenation of a Core Phosphorus Atom, J. Org. Chem., 75, 2, 375-389, 2010.01.
36. T. Sakata, Y. Kawashima, and H. Nakano, New Sampling Scheme for Combined Quantum Mechanical and Molecular Mechanical Simulation, Kyushu University Global-COE program, Science for Future Molecular Systems, Journal, 3, 13-20, 2009.12.
37. T. Sakata, Y. Kawashima, and H. Nakano, Low-Lying Excited States of 7-Aminocoumarin Derivatives: A Theoretical Study, Int. J. Quantum Chem. , 109, 9, 1940-1949, 2009.08.
38. H. Moriyama, H. Tatewaki, Y. Watanabe, and H. Nakano, Molecular spinors suitable for four-component relativistic correlation calculations: studies of LaF+ and LaF using multiconfigurational quasi-degenerate perturbation theory, Int. J. Quantum Chem. , 109, 9, 1898-1904, 2009.08.
39. N. Noguchi and H. Nakano, Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories, J. Chem. Phys., 130, 15, 154309 , 2009.04.
40. Y. Matano, T. Nakabuchi, S. Fujishige, H. Nakano, and H. Imahori, Redox-Coupled Complexation of 23-Phospha-21-thiaporphyrin with Group 10 Metals: A Convenient Access to Stable Core-Modified Isophlorin-Metal Complexes, J. Am. Chem. Soc. , 130, 49, 16446-16447, 2008.12.
41. H. Tatewaki, S. Yamamoto, Y. Watanabe, H. Nakano , Electronic structure of CeF from frozen-core four-component relativistic multiconfigurational quasidegenerate perturbation theory
, J. Chem. Phys., 128, 214901/1-8, 2008.06.
42. H. Moriyama, Y. Watanabe, H. Nakano, H. Tatewaki , Electronic Structure of LaF+ and LaF from Frozen-Core Four-Component Relativistic Multiconfigurational Quasidegenerate Perturbation Theory
, J. Phys. Chem. A, 112, 2683-2692 (2008), 2008.03.
43. Y. Matano, M. Nakashima, T. Nakabuchi, H. Imahori, S. Fujishige, H. Nakano , Monophosphaporphyrins: Oxidative pi-Extension at the Peripherally Fused Carbocycle of the Phosphaporphyrin Ring
, Org. Lett., 10, 553-556, 2008.02.
44. J. Saito, K. Ara, K. Sugiyama, H. Kitagawa, H. Nakano, K. Ogata, N. Yoshioka, Study on Chemical Reactivity Control of Liquid Sodium - Development of Nano-Fluid and its Property, and Applicability to FBR Plant, ICONE16: Proceeding of the 16th International Conference on Nuclear Engineering, 1, 559-563, 2008.01.
45. Y. Matano, T. Shinokura, K. Matsumoto, H. Imahori, H. Nakano , Synthesis and Aggregation Behavior of meso-Sulfinylporphyrins: Evaluation of S-Chirality Effects on the Self-Organization to S-Oxo-Tethered Cofacial Porphyrin Dimers, Chem. Asian J., 2, 1417-1429 , 2007.08.
46. X. Zhang, Y. Komoto, K. Sakota, M. Nakagaki, T. Shinmyozu, S. Nanbu, H. Nakano, H. Sekiya , Remarkable suppression of the excited-state double-proton transfer in the 7-azaindole dimer due to substitution of the dimethylamino group studied by electronic spectroscopy in the gas phase
, Chem. Phys. Lett., 443, 194-198 , 2007.08.
47. R. Ebisuzaki, Y. Watanabe, H. Nakano, Efficient implementation of relativistic and non-relativistic quasidegenerate perturbation theory with general multiconfigurational reference functions
, Chem. Phys. Lett., 442, 164-169, 2007.07.
48. X. Zhang, Y. Komoto, K. Sakota, M. Nakagaki, H. Nakano, T. Shinmyozu, H. Sekiya, Heavy mass effect on excited-state double-proton transfer in the 7-azaindole dimer by Cl substitution, Chem. Phys. Lett., 441, 176-180 , 2007.06.
49. Y. Watanabe, H. Nakano, H. Tatewaki, Effect of removing the no-virtual-pair approximation on the correlation energy of the He isoelectronic sequence
, J. Chem. Phys. , 126, 174105 , 2007.05.
50. Y. Matano, T. Nakabuchi, T. Miyajima, H. Imahori, H. Nakano, Synthesis of Hybrid Phosphorus-Containing Porphyrin
, Org. Lett., 8, 5713-5716 , 2006.11.
51. H. Nakano, Multireference Perturbation Theory with Four-Component General Multiconfigurational Reference Functions, Recent Progress in Computational Sciences and Engineering, 7, 931-934, 2006.10.
52. M. Nakagaki, E. Nishi, K. Sakota, H. Nakano, H. Sekiya, A model two-dimensional potential for internal rotation of 9-methylanthracene studied by electronic spectroscopy and DFT calculations, Chem. Phys., 328, 190-196 , 2006.07.
53. S. Yamamoto, H. Tatewaki, H. Moriyama, H. Nakano, A study of the ground state of manganese dimer using quasidegenerate perturbation theory
, J. Chem. Phys., 124, 124302 , 2006.04.
54. M. Miyajima, Y. Watanabe, H. Nakano, Relativistic quasidegenerate perturbation theory with four-component general multiconfiguration reference functions
, J. Chem. Phys., 124, 044101 , 2006.01.
55. M. Nakagaki, E. Nishi, K. Sakota, K. Nishi, H. Nakano, H. Sekiya, Internal rotation of methyl group in 2- and 1-methylanthracene studied by electronic spectroscopy and DFT calculations, Chem. Phys., 10.1016/j.chemphys.2005.06.006, 316, 1-3, 178-184, 316, 178-184, 2005.07.
56. H. Sato, A. Yamagishi, J. Yoshida, H. Nakano, and N. Hoshino, A Microscopic Model for Helical Twisting Power by the Optical Isomers of an Octahedral Metal Complex, Jpn. J. Appl. Phys., 10.1143/JJAP.44.4067, 44, 6A, 4067-4072, 44, 4067-4072, 2005.01.
57. Y. Kurashige, H. Nakano, and K. Hirao, The Most Stable Structure of SiC3 Studied by Multireference Perturbation Theory with General Multiconfiguration Self-Consistent Field Reference Functions, J. Phys. Chem. A, 108, 3064-3067 (2004), 2004.04.
58. Y. Kurashige, H. Nakano, Y. Nakao, and K. Hirao, The pi->pi* excited states of long linear polyenes studied by the CASCI-MRMP method, Chem. Phys. Lett., 10.1016/j.cplett.2004.10.141, 400, 4-6, 425-429, 400, 425-429, 2004.01.
59. Y. Matano, H. Nomura, T. Hisanaga, H. Nakano, M. Shiro, and H. Imahori, Diverse Structures and Remarkable Oxidizing Ability of Triarylbismuthane Oxides. Comparative Study on the Structure and Reactivity of a Series of Triarylpnictogen Oxides, Organometallics, 10.1021/om0494115, 23, 23, 5471-5480, 23, 5471-5480, 2004.01.
60. Y. Kobayashi, N. Tajima, H. Nakano, and K. Hirao, Selective Catalytic Reduction of Nitric Oxide by Ammonia: The Activation Mechanism, J. Phys. Chem. B, 108, 12264-12266 (2004), 2004.01.
61. T. Yanai, H. Nakano, T. Nakajima, T. Tsuneda, S. Hirata, Y. Kawashima, Y. Nakao, M. Kamiya, H. Sekino, and K. Hirao, UTChem - A Program for ab initio Quantum Chemistry, Proceedings of Computational Science - ICCS 2003, Lecture Notes in Computer Science, Vol. 2660, edited by P. M. A. Sloot, D. Abramson, A. Bogdanov, J. J. Dongarra, A. Zomaya, and Y. Gorbachev (Springer-Verlag, Berlin, 2003), pp. 84-95, 2003.01.
62. H. Sato, A. Morita, K. Ono, H. Nakano, N. Wakabayashi, and A. Yamagishi, Templating Effects on the Mineralization of Layered Inorganic Compounds: (1) Density Functional Calculations of the Formation of Single-Layered Magnesium Hydroxide as a Brucite Model, Langmuir, 19, 7120-7126 (2003), 2003.01.
63. H. Nakano and K. Hirao, Recent Advances in Multireference-Based Perturbation Theory, Bull. Korean Chem. Soc., 24, 812-816 (2003), 2003.01.
64. H. A. Witek, H. Nakano, and K. Hirao, Multireference perturbation theory with optimized partitioning. I. Theoretical and computational aspects, J. Chem. Phys., 118, 8197-8206 (2003), 2003.01.
65. H. A. Witek, H. Nakano, and K. Hirao, Multireference Perturbation Theory with Optimized Partitioning. II. Applications to Molecular Systems, J. Comput. Chem., 24, 1390-1400 (2003), 2003.01.
66. K. Yokoyama, H. Nakano, K. Hirao, and J. P. Finley, Maximum radius of convergence perturbation theory: test calculations on Be, Ne, H2 and HF, Theor. Chem. Acc., 110, 185-189 (2003), 2003.01.
67. K. Sorakubo, T. Yanai, K. Nakayama, M. Kamiya, H. Nakano, and K. Hirao, A non-orthogonal Kohn-Sham method using partially fixed molecular orbitals, Theor. Chem. Acc., 110, 328-337 (2003), 2003.01.
68. T. Nakajima, T. Tsuneda, H. Nakano, and K. Hirao, Recent Advances in Electronic Structure Theory, J. Theor. Comput. Chem., 1, 109-136 (2002), 2002.01.
69. H. Nakano, R. Uchiyama, and K. Hirao, Quasi-degenerate perturbation theory with general multiconfiguration self-consistent field reference functions, J. Comput. Chem., 23, 1166-1175 (2002), 2002.01.
70. Y. Matano, H. Nomura, H. Suzuki, M. Shiro, and H. Nakano, Synthesis, Structure, and Reactions of (Acylimino)triaryl-lambda5-bismuthanes: First Comparative Study of the (Acylimino)pnictorane Series, J. Am. Chem. Soc., 123, 10954-10965 (2001), 2001.01.
71. K. Takeda, T. Tsuchiya, H. Nakano, T. Taketsugu, and K. Hirao, Stability of multiply charged anions of lanthanide hexafluorides LnF62- and LnF63- (Ln=Ce to Lu), J. Mol. Struct. (Theochem), (Fraga Special Issue), 537, 107-115 (2001), 2001.01.
72. H. Nakano, J. Nakatani, and K. Hirao, Second-order quasi-degenerate perturbation theory with quasi-complete active space self-consistent field reference functions, J. Chem. Phys., 114, 1133-1141 (2001), 2001.01.
73. H. Nakano, T. Nakajima, T. Tsuneda, and K. Hirao, Research activities of the theoretical chemistry group at the University of Tokyo, J. Mol. Struct. (Theochem), 573, 91-128 (2001), 2001.01.
74. Y. Kobayashi, H. Nakano, and K. Hirao, Multireference Moller-Plesset perturbation theory using spin-dependent orbital energies, Chem. Phys. Lett., 336, 529-535 (2001), 2001.01.
75. Y.-K. Choe, J. P. Finley, H. Nakano, and K. Hirao, On the performance of diagrammatic complete active space perturbation theory, J. Chem. Phys., 113, 7773-7778 (2000), 2000.01.
76. T. Yanai, K. Ishida, H. Nakano, and K. Hirao, New algorithm for electron repulsion integrals oriented to the general contraction scheme, Int. J. Quantum Chem., 76, 396-406 (2000), 2000.01.
77. H. Nakano and K. Hirao, A quasi-complete active space self-consistent field method, Chem. Phys. Lett., 317, 90-96 (2000), 2000.01.
78. K. R. Glaesemann, M. S. Gordon, and H. Nakano, A study of FeCO+ with correlated wavefunctions, Phys. Chem. Chem. Phys., 1, 6, 967-976, 1999.03.
79. Y. Kawashima, T. Hashimoto, H. Nakano, and K. Hirao, Theoretical study of the valence pi -> pi* excited states of polyacenes: anthracene and naphthacene, Theor. Chem. Acc., 102 (Fukui Memorial Issue), 49-64 (1999), 1999.01.
80. T. Hashimoto, Y.-K. Choe, H. Nakano, and K. Hirao, Theoretical study of the Q and B bands of free-base, magnesium, and zinc porphyrins, and their derivatives, J. Phys. Chem. A, 103, 1894-1904 (1999), 1999.01.
81. T. Tsuchiya, T. Taketsugu, H. Nakano, and K. Hirao, Theoretical study of electronic and geometric structures of a series of lanthanide trihalaides LnX3 (Ln = La-Lu; X = Cl, F), J. Mol. Struct. (Theochem), 461-462 (Morokuma Special Issue), 203-222 (1999), 1999.01.
82. Y. Tsurutani, S. Machida, K. Horie, Y. Kawashima, H. Nakano, and K. Hirao, Fluorescence and photoinversion reactions in solutions of chiral diaryl sulfoxides with various sizes of aromatic rings, J. Photochem. Photobiol. A, 122, 161-168 (1999), 1999.01.
83. H. Nakano, K. Nakayama, and K. Hirao, Complete active space valence bond method applied to chemical reactions, J. Mol. Struct. (Theochem), 461-462 (Morokuma Special Issue), 55-69 (1999), 1999.01.
84. T. Hashimoto, H. Nakano, and K. Hirao, Theoretical study of valence and Rydberg excited states of benzene revisited, J. Mol. Struct. (Theochem), 451 (Huzinaga Special Issue), 25-33 (1998), 1998.01.
85. K. Nakayama, H. Nakano, and K. Hirao, Theoretical study of the pi -> pi* excited states of linear polyenes: The energy gap between 11Bu and 21Ag states and their character, Int. J. Quantum Chem., 66, 157-175 (1998), 1998.01.
86. Y.-K. Choe, T. Hashimoto, H. Nakano, and K. Hirao, Theoretical study of the electronic ground state of Iron (II) porphine, Chem. Phys. Lett., 295, 380-388 (1998), 1998.01.
87. H. Nakano, K. Hirao, and M. S. Gordon, Analytic energy gradients for multiconfigurational self-consistent field second-order quasidegenerate perturbation theory (MC-QDPT), J. Chem. Phys., 108, 5660-5669 (1998), 1998.01.
88. K. Hirao, H. Nakano, and K. Nakayama, A complete active valence bond method with nonorthogonal orbitals, J. Chem. Phys., 107, 23, 9966-9974, 1997.12.
89. M. S. Gordon, T. J. Barton, and H. Nakano, Ring opening of silacyclobutane, J. Am. Chem. Soc., 119, 49, 11966-11973, 1997.12.
90. H. Nakano, K. Nakayama, K. Hirao, and M. Dupuis, Transition state barrier height for H2CO -> H2 + CO reaction by multireference Moller-Plesset perturbation theory, J. Chem. Phys., 106, 12, 4912-4917, 1997.03.
91. Y. Kawashima, K. Nakayama, H. Nakano, and K. Hirao, Theoretical study of the pi -> pi* excited states of linear polyene radical cations and dications, Chem. Phys. Lett., 267, 1-2, 82-90 , 1997.03.
92. K. Hirao, H. Nakano, K. Nakayama, and M. Dupuis, A complete active space valence bond (CASVB) method, J. Chem. Phys., 105, 20, 9227-9239, 1996.11.
93. H. Hashimoto, H. Nakano, and K. Hirao, Theoretical study of the singlet and triplet pi -> pi* excited states of polyacenes: Benzene and naphthalene, J. Chem. Phys., 104, 16, 6244-6258, 1996.04.
94. H. Nakano, T. Tsuneda, T. Hashimoto, and K. Hirao, Theoretical study of the excitation spectra of five-membered ring compounds: Cyclopentadiene, furan, and pyrrole, J. Chem. Phys., 104, 6, 2312-2320, 1996.02.
95. K. Hirao, H. Nakano, and T. Hashimoto, Multireference Moller-Plesset perturbation treatment for valence and Rydberg excited states of benzene, Chem. Phys. Lett., 235, 5-6, 430-435 , 1995.03.
96. T. Tsuneda, H. Nakano, and K. Hirao, Study of low-lying electronic states of ozone by multireference Moller-Plesset perturbation method, J. Chem. Phys., 103, 15, 6520-6528, 1995.10.
97. H. Nakano, Quasidegenerate perturbation theory with multiconfigurational self-consistent-field reference functions, J. Chem. Phys., 99, 7983-7992, 1993.11.
98. H. Nakano, MCSCF reference quasidegenerate perturbation theory with Epstein-Nesbet partitioning, Chem. Phys. Lett., 207, 4-6, 372-378, 1993.05.
99. H. Nakano and S. Obara, Convergence property of multireference many-body perturbation theory analyzed by the use of a norm of effective Hamiltonian, Theor. Chim. Acta,, 86, 369-377, 1993.01.
100. H. Nakano, T. Nakajima, and S. Obara, Efficient and stable method of searching for optimum structures of molecules containing cyclic parts, Chem. Phys. Lett., 177, 458-462 (1991), 1991.01.
101. Y. Matano, D. Fujii, T. Shibano, K. Furukawa, T. Higashino, H. Nakano, H. Imahori, Covalently Linked 5,15-Diazaporphyrin Dimers: Promising Scaffolds for Highly Conjugated Azaporphyrin pi-System, Chem. Eur. J..
102. Y. Kasai, N. Yoshida, H. Nakano, Theoretical analysis of salt effect on intramolecular proton transfer reaction of glycine in NaCl aqueous solution, J. Mol. Liq..