Kyushu University Academic Staff Educational and Research Activities Database
List of Papers
Motoki Toganoh Last modified date:2021.06.23

Assistant Professor / Organic Functional Molecular Chemistry / Department of Applied Chemistry / Faculty of Engineering

1. Ishizuka, Tomoya; Sakashita, Ryuichi; Iwanaga, Osamu; Morimoto, Tatsuki; Mori, Shigeki; Ishida, Masatoshi; Toganoh, Motoki; Takegoshi, Kiyonori; Osuka, Atsuhiro; Furuta, Hiroyuki, NH Tautomerism of N-Confused Porphyrin: Solvent/Substituent Effects and Isomerization Mechanism, JOURNAL OF PHYSICAL CHEMISTRY A, 10.1021/acs.jpca.0c04779, 124, 28, 5756-5769, 2020.07.
2. Yamamoto, Takaaki; Abraham, Jibin Alex; Mori, Shigeki; Toganoh, Motoki; Shimizu, Soji; Ishida, Masatoshi; Furuta, Hiroyuki, Tungsten(VI) Complex of N-Fused Porphyrin Absorbing Near-Infrared Light beyond 1000 nm, CHEMISTRY-AN ASIAN JOURNAL, 10.1002/asia.202000014, 15, 6, 748-752, 2020.03.
3. Motoki Toganoh, Hiroyuki Furuta, N-fused porphyrin
A maverick member of the porphyrin family, Chemistry Letters, 10.1246/cl.190250, 48, 7, 615-622, 2019.01, Fusion is a relatively new concept to produce unique members of the porphyrin family. A representative compound formed by fusion is Nfused porphyrin, which is synthesized from N-confused porphyrin. N-Fused porphyrin has an unusually narrow HOMOLUMO energy gap and exhibits absorption in the near infrared region up to 1100 nm. Moreover, N-fused porphyrin serves as a versatile mononegative tridentate ligand, which can bind a variety of metal centers tightly. While inner-core fusion is rare in tetrapyrrolic porphyrinoids, it becomes more common in expanded porphyrins, where a variety of novel structures are produced unanticipatedly..
4. Hisamune, Y.; Kim, T.: Nishimura, K.; Ishida, M.; Toganoh, M.; Mori, S.; Kim, D.; Furuta, H., Switch-ON Near IR Fluorescent Dye Upon Protonation: Helically Twisted Bis(Boron Difluoride) Complex of -Extended Corrorin, CHEMISTRY-A EUROPEAN JOURNAL, 10.1002/chem.201705516, 24, 18, 4628-4634, 2018.04.
5. Matsuo, H.; Toganoh, M.; Ishida, M.; Mori, S.; Furuta, H., Stereoretentive Ligand Exchange Reactions of N-Fused Porphyrin Ruthenium(II) Complexes, INORGANIC CHEMISTRY, 10.1021/acs.inorgchem.7b01972, 56, 22, 13842-13851, 2017.11.
6. Sakashita, R.; Oka, Y.; Akimaru, H.; Kesavan, P.; Ishida, M.; Toganoh, M.; Ishizuka, T.; Mori, S.; Furuta, H., Tautomerism-Induced Cis-Trans Isomerization of Pyridylethenyl N-Confused Porphyrin, JOURNAL OF ORGANIC CHEMISTRY, 10.1021/acs.joc.7b01770, 82, 16, 8686-8696, 2017.08.
7. Masatoshi Ishida, Hiroyuki Fujimoto, Tatsuki Morimoto, Shigeki Mori, Motoki Toganoh, Soji Shimizu, Furuta, H, Supramolecular dimeric structures of pyrazole-containing meso-oxo carbaphlorin analogues, SUPRAMOLECULAR CHEMISTRY, 10.1080/10610278.2016.1158408, 29, 1, 8-16, 2017.01.
8. Masatoshi Ishida, Toshihiro Omagari, Ryuji Hirosawa, Keisuke Jono, Yong Mo Sung, Yuhsuke Yasutake, Hidemitsu Uno, Motoki Toganoh, Nakanotani Hajime, Susumu Fukatsu, Dongho Kim, Hiroyuki Furuta, Boron Difluoride Complexes of Expanded N-Confused Calix[n]phyrins That Demonstrate Unique Luminescent and Lasing Properties, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 10.1002/anie.201606246, 55, 39, 12045-12049, 2016.09.
9. Motoki Toganoh, Hideaki Matsuo, Furuta, H, Ruthenocene-Type Complexes of N-Fused Porphyrins, CHEMISTRY-A EUROPEAN JOURNAL, 10.1002/chem.201600813, 22, 24, 8316-8322, 2016.06.
10. Yogesh Kumar Maurya, Takahiro Ishikawa, Yasunori Kawabe, Masatoshi Ishida, Motoki Toganoh, Shigeki Mori, Yuhsuke Yasutake, Susumu Fukatsu, Furuta, H, Near-Infrared Phosphorescent Iridium(III) Benzonorrole Complexes Possessing Pyridine-based Axial Ligands, INORGANIC CHEMISTRY, 10.1021/acs.inorgchem.6b00853, 55, 12, 6223-6230, 2016.06.
11. Gokulnath, Sabapathi; Nishimura, Keiichi; Toganoh, Motoki; Mori, Shigeki; Furuta, Hiroyuki, Palladium-Induced Pyrrolic Rearrangement of a Singly to a Doubly N-Confused [26]Hexaphyrin, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 10.1002/anie.201302955, 52, 27, 6940-6943, 2013.11.
12. Toganoh, Motoki; Furuta, Hiroyuki, Theoretical Study on the Conformation and Aromaticity of Regular and Singly N-Confused [28]Hexaphyrins, JOURNAL OF ORGANIC CHEMISTRY, 10.1021/jo401531w, 78, 18, 9317-9327, 2013.09.
13. Toganoh, Motoki; Matsuo, Hideaki; Sato, Ayumi; Hirashima, Yuya; Furuta, Hiroyuki, Synthesis and Isomerization of N-Fused Tetraphenylporphyrin Ruthenium(II) Complexes, INORGANIC CHEMISTRY, 10.1021/ic401314a, 52, 16, 9613-9619, 2013.08.
14. Toganoh, Motoki; Harada, Naoyuki; Furuta, Hiroyuki, Flexible coordination of hetero-scorpionate ligands composed of pyrrole/pyridines hybrid in rhenium(I) tricarbonyl complexes, POLYHEDRON, 10.1016/j.poly.2012.06.053, 52, 1153-1158, 2013.03.
15. Takaaki Yamamoto, Motoki Toganoh, Shigeki Mori, Hidemitsu Uno, Hiroyuki Furuta, Rhenium complexes of peripherally pi-extended N-confused porphyrins, CHEMICAL SCIENCE, 10.1039/c2sc20708g, 3, 11, 3241-3248, 2012.11.
16. Satoshi Touden, Ikawa Yoshiya, Ryuichi Sakashita, Motoki Toganoh, Shigeki Mori, Hiroyuki Furuta, Sulfur-assisted interconversion between N-confused porphyrin and N-fused porphyrin, TETRAHEDRON LETTERS, 10.1016/j.tetlet.2012.08.131, 53, 45, 6071-6074, 2012.11.
17. Motoki Toganoh, Yasunori Kawabe, Hidemitsu Uno, Hiroyuki Furuta, Unique Interaction between Directly Linked Laminated p Planes in the Benzonorrole Dimer, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 10.1002/anie.201203712, 51, 35, 8753-8756, 2012.08.
18. Maira Fasciotti, Alexandre F. Gomes, Fabio C. Gozzo, Bernardo A. Iglesias, Gilberto F. de Sa, Romeu J. Daroda, Motoki Toganoh, Hiroyuki Furuta, Koiti Araki, Marcos N. Eberlin, Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry, ORGANIC & BIOMOLECULAR CHEMISTRY, 10.1039/c2ob26209f, 10, 42, 8396-8402, 2012.08.
19. Motoki Toganoh, Takaaki Yamamoto, Takayoshi Hihara, Hisanori Akimaru, Hiroyuki Furuta, Regulation of NH-tautomerism in N-confused porphyrin by N-alkylation, ORGANIC & BIOMOLECULAR CHEMISTRY, 10.1039/c2ob25351h, 10, 22, 4367-4374, 2012.04.
20. Takaaki Yamamoto, Motoki Toganoh, Hiroyuki Furuta, Cooperation between metal and ligand in oxygen atom transport by N-confused porphyrin oxorhenium(V) complexes, DALTON TRANSACTIONS, 10.1039/c2dt30885a, 41, 30, 9154-9157, 2012.04.
21. Motoki Toganoh, Sabapathi Gokulnath, Yasunori Kawabe, Hiroyuki Furuta, Synthesis and reactivity of 5,10,15-triaryl doubly N-confused bilanes, Chemistry - A European Journal, 10.1002/chem.201103034, 18, 14, 4380-4391, 2012.04, A series of 5,10,15-tris(pentafluorophenyl) doubly N-confused bilanes were synthesized in a stepwise manner with the aid of sterically demanding N-protecting groups, in which the difference in reactivity between regular pyrrole and N-confused pyrrole plays a crucial role in the synthetic strategy. Some doubly N-confused bilanes were converted into porphyrinoids or a unique 2:2 copper(II) complex with a helical structure. In addition, the conformations and electronic states of the doubly N-confused bilanes were investigated theoretically, giving fruitful information about the effect of confusion on the bilane skeleton..
22. Sabapathi Gokulnath, Motoki Toganoh, Yamaguchi Keisuke, Shigeki Mori, Hidemitsu Uno, Hiroyuki Furuta, Confusion of Mobius aromaticity: disruption of annulenic pathway in singly N-confused [28]hexaphyrin and its mono-Pd(II) complex, DALTON TRANSACTIONS, 10.1039/c2dt30306j, 41, 20, 6283-6290, 2012.03.
23. Motoki Toganoh, Hiroyuki Furuta, Blooming of confused porphyrinoids-fusion, expansion, contraction, and more confusion, CHEMICAL COMMUNICATIONS, 10.1039/c1cc14633e, 48, 7, 937-954, 2012.01.
24. Motoki Toganoh, Yasunori Kawabe, Hiroyuki Furuta, C-fused norrole
A fused corrole isomer bearing a N,C-linked bipyrrole unit, Journal of Organic Chemistry, 10.1021/jo2014017, 76, 18, 7618-7622, 2011.09, Oxidative cyclization of a doubly N-confused bilane afforded a N-confused N,C-linked corrole (N-confused norrole), which was readily oxidized to form a C-fused N,C-linked corrole (C-fused norrole)..
25. Motoki Toganoh, Takumi Takayama, Nandy Ritesh, Nobuo Kimizuka, Hiroyuki Furuta, Synthesis and properties of acetylene-bridged N-confused porphyrin dimers, Chemistry Letters, 10.1246/cl.2011.1021, 40, 9, 1021-1023, 2011.09, Acetylene-bridged N-confused porphyrin (NCP) dimers were synthesized by Stille coupling reactions. Moderate electronic interaction between the NCP chromophores was observed in the inner-3H tautomers while strong interaction was observed in the inner-2H tautomers..
26. Keitaro Fujino, Yasuyuki Hirata, Yasunori Kawabe, Tatsuki Morimoto, Alagar Srinivasan, Motoki Toganoh, Yugo Miseki, Akihiko Kudo, Hiroyuki Furuta, Confusion and neo-confusion
Corrole isomers with an NNNC core, Angewandte Chemie - International Edition, 10.1002/anie.201100429, 50, 30, 6855-6859, 2011.07, More confused than ever: Three types of N-confused corrole isomers (NCCs) were synthesized, and the structures of these isomers were revealed by single-crystal X-ray crystallography. The position of the confused pyrrole ring in the NCC has a pronounced effect on optical and anion-binding properties..
27. Shinya Ikeda, Motoki Toganoh, Hiroyuki Furuta, Synthesis, reactivity, and properties of N-fused porphyrin manganese(I) tricarbonyl complexes, Inorganic chemistry, 10.1021/ic2000393, 50, 13, 6029-6043, 2011.07, The reactions of N-fused tetraphenylporphyrin (NFTPP, 1a) and its 21-substituted derivatives, 21-Br-NFTPP (1b), 21-NO2-NFTPP (1c), and 21-Bz-NFTPP (1d), with Mn(CO)5Br gave the manganese(I) tricarbonyl complexes bearing N-fused tetraphenylporphyrinato ligands (2a-d), respectively, in 46-99% yields. The complexes were characterized by mass, IR, 1H and 13C NMR spectroscopy, and the final structural proof was evident from the X-ray crystallographic analysis for 2a. The crystals of 2a•CH 2Cl2 belong to the monoclinic space group P21/n (#14), with a = 15.007(2) Å, b = 12.5455(19) Å, c = 21.150(3) Å, β = 102.227(4)°, and Z = 4. The lengths (Å) of three manganese-nitrogen and three manganese-carbon bonds are inequivalent respectively [Mn-N(2), 2.007(2); Mn-N(23), 2.033(2); Mn-N(24), 1.988(3); and Mn-CO, 1.798(4), 1.804(4), 1.841(3)], reflecting the asymmetric structure of the NFp ligand. The aromatic substitution reactions of 2a, such as nitration, formylation, and chlorination, proceeded without a loss of center metal to give the corresponding 21-nitro (2c), 21-formyl (2e), and 21-chloro (2f) derivatives, regioselectively. In the electrochemical measurements of 2, one reversible oxidation and two reversible reduction waves were observed. The redox potentials of 2 indicate the narrow energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO) being consistent with the electronic absorption spectra that display the absorption edges over 1000 nm. Protonation occurred at the inner core nitrogen of 2a upon the addition of acids, which is inferred from the 1H NMR spectra as well as theoretical calculations. By a treatment with amine N-oxides, demetalation of 2 proceeded to afford the corresponding NFP free-bases (1)..
28. Motoki Toganoh, Ayumi Sato, Hiroyuki Furuta, Double-decker ferrocene-type complex of N-fused porphyrin
A model of π-extended ferrocene?, Angewandte Chemie - International Edition, 10.1002/anie.201007940, 50, 12, 2752-2755, 2011.03, Whopper sandwich: A double-decker ferrocene-type complex with N-fused porphyrinato ligands (see picture) was synthesized from N-fused porphyrin, and its structure and properties were characterized with X-ray crystallographic analysis, variable-temperature 1H NMR spectra, and electrochemical measurements. The unique three-dimensional d-π conjugated system was elucidated with the aid of DFT studies..
29. Sabapathi Gokulnath, Keisuke Yamaguchi, Motoki Toganoh, Shigeki Mori, Hidemitsu Uno, Hiroyuki Furuta, Singly N-confused [26]hexaphyrin
A binucleating porphyrinoid ligand for mixed metals in different oxidation states, Angewandte Chemie - International Edition, 10.1002/anie.201006784, 50, 10, 2302-2306, 2011.03, (Chemical Equation Presented) Mix and match: The title porphyrinoid has been synthesized and shows unique coordination chemistry by incorporating two different metals with different oxidation states (see figure). X-ray crystallography was used to confirm that a rectangular conformation in both mono- and binuclear complexes was retained..
30. Shinya Ikeda, Motoki Toganoh, Shanmugam Easwaramoorthi, Jong Min Lim, Dongho Kim, Hiroyuki Furuta, Synthesis and photophysical properties of N-fused tetraphenylporphyrin derivatives
Near-infrared organic dye of [18]annulenic compounds, Journal of Organic Chemistry, 10.1021/jo102128m, 75, 24, 8637-8649, 2010.12, A variety of N-fused porphyrin derivatives were prepared and their photophysical properties were investigated. Although intact N-fused tetraarylporphyrins showed almost no emission, introduction of electron-withdrawing groups such as a nitro group and a cyano group on the macrocycles caused significant refinements in their emission efficiency. Long emission wavelengths (900-1000 nm) as well as fairly large Stokes shifts (∼1200 cm-1) are exceptionally unique photophysical properties among [18]annulenic compounds, which could be rationalized by the excited state intramolecular proton transfer (ESIPT) process. Relatively weak emission quantum yields (∼5.0 × 10-4) and unusually short S1 state lifetimes (∼13.5 ps) are in good agreement with the ESIPT process. The solvent and substituent effects on the photophysical properties are also discussed in conjunction with the theoretical studies, where the mesityl groups at the meso-positions play a unique role..
31. Motoki Toganoh, Hiroyuki Furuta, Theoretical study on conformation and electronic state of Hückel-aromatic multiply N-confused [26]hexaphyrins, Journal of Organic Chemistry, 10.1021/jo101856h, 75, 23, 8213-8223, 2010.12, Conformations and electronic states of Hückel-aromatic regular, singly, doubly, and triply N-confused [26]hexaphyrins were investigated using density functional theory (DFT) calculations. A comparison of the molecular energies of 754 structures in all revealed that the most stable conformers depend on the degree of confusion, where ring strain and intramolecular hydrogen bonding would play a critical role. Consequently, regular and singly N-confused hexaphyrins prefer a dumbbell conformation, doubly N-confused hexaphyrin prefers a rectangular conformation, and triply N-confused hexaphyrin prefers a triangular conformation. Introduction of N-confused pyrrole rings into the hexaphyrin framework causes narrower HOMO-LUMO energy gaps, while it does not affect the NICS values or aromaticity significantly. The steric repulsion imposed by meso-aryl substituents largely affects the relative energies among the conformers..
32. Motoki Toganoh, Takayoshi Hihara, Hiroyuki Furuta, N-heterocyclic carbene embedded in an N-confused porphyrin framework, Inorganic Chemistry, 10.1021/ic1016356, 49, 18, 8182-8184, 2010.09, A rhenium(I) complex of an N-heterocyclic carbene ligand embedded in an N-confused porphyrin core was serendipitously synthesized by the reaction of an inner-methylated N-confused porphyrin with Re2(CO)10..
33. Motoki Toganoh, Hiroyuki Harada, Yoshiya Ikawa, Hiroyuki Furuta, Self-assembly of Zn(II) porphyrin-1,2,3-triazole conjugate with alcohol glue, Chemistry Letters, 10.1246/cl.2010.252, 39, 3, 252-253, 2010.03, A Zn(II) porphyrin-1,2,3-triazole conjugate (1-Zn), which can be prepared by click chemistry, afforded a unique self-assembled structure with methanol molecules as glue in the crystals and in toluene solution. The resulting assembled units form a zigzag architecture due to multipoint CH-π interactions in the solid state..
34. Jae Seok Lee, Jong Min Lim, Motoki Toganoh, Hiroyuki Furuta, Dongho Kim, Comparative spectroscopic studies on porphyrin derivatives
Electronic perturbation of N-confused and N-fused porphyrins, Chemical Communications, 10.1039/b916521e, 46, 2, 285-287, 2010.02, N-confused and N-fused porphyrins revealed quite unique photophysical properties arising from their perturbed π-conjugation pathways induced by structural modifications such as confusion and fusion of pyrrole rings compared with their parent porphyrin molecules..
35. Jong Min Lim, Jae Seok Lee, Hyun Woo Chung, Hee Won Bahng, Keisuke Yamaguchi, Motoki Toganoh, Hiroyuki Furuta, Dongho Kim, Photophysical properties of N-confused hexaphyrins
Effects of confusion of pyrrole rings and molecular shape on electronic structures, Chemical Communications, 10.1039/c0cc00001a, 46, 24, 4357-4359, 2010.04, Doubly and triply N-confused hexaphyrins revealed quite unique photophysical properties arising from confusion of pyrrole rings in the macrocycle, and the molecular shape when compared with their parent regular hexaphyrin molecules..
36. Motoki Toganoh, Hiroyuki Furuta, Theoretical study on rotation of pyrrole rings in porphyrin and N-confused porphyrin, Journal of Physical Chemistry A, 10.1021/jp906126g, 113, 50, 13953-13963, 2009.12, Rotation of pyrrole rings in regular porphyrins and N-confused porphyrins is theoretically investigated by DFT calculations. While the inversion of the pyrrole rings in the regular porphyrins requires high activation energies (36.5-49.1 kcal/mol), the inversion of the confused pyrrole rings in the N-confused porphyrins requires much lower activation energies (18.1-24.5 kcal/mol). This marked difference can be explained by the intramolecular hydrogen bondings and aromatic stabilization due to the [18]annulenic substructures, where confusion and NH tautomerism play an important role. In both of the macrocycles, 360° rotation of their pyrrole rings would be difficult possibly due to the small cavity. Alternatively, a reaction pathway for the production of N-fused porphyrin from. N-confused porphyrin is obtained, which is consistent with the experimental, observation..
37. Motoki Toganoh, Hiroaki Ogawa, Tatsuki Morimoto, Hiroyuki Furuta, Programmed asymmetrical trimer formation of β-alkyl N-confused porphyrin zinc(II) complex, Supramolecular Chemistry, 10.1080/10610270802588293, 21, 3-4, 324-330, 2009.11, Self-coordination of β-alkyl N-confused porphyrin (NCP) zinc(II) complexes has been studied to reveal that asymmetrical trimers formed exclusively. A key factor to control the configuration of the trimers (symmetric or asymmetric) has been studied theoretically, and revealed that the steric environment around the peripheral nitrogen atoms as well as rotational angles of the confused pyrrole rings play a crucial role in trimer formation of β-alkyl NCP zinc(II) complexes..
38. Motoki Toganoh, Hironao Miyachi, Hisanori Akimaru, Fuyuki Ito, Toshihiko Nagamura, Hiroyuki Furuta, Anion responsive dyad system of porphyrin and N-confused porphyrin, Organic and Biomolecular Chemistry, 10.1039/b907775h, 7, 15, 3027-3030, 2009.08, A dyad of porphyrin and N-confused porphyrin is synthesized for the first time, in which an efficient excitation energy transfer as well as enhancement of emission quantum yield induced by anion binding is observed..
39. Dong Hoon Won, Motoki Toganoh, Hidemitsu Uno, Hiroyuki Furuta, Pt(II) N-confused porphyrin
An expanded pyrrole that affords a stable π-anion, Dalton Transactions, 10.1039/b906018a, 31, 6151-6158, 2009.08, Pt(II) complex of meso-tetrakis(pentafluorophenyl) N-confused porphyrin (1-Pt) efficiently binds Cl-, Br-, and I- anions at the peripheral N-H, while deprotonation proceeds with F-, H2PO4-, and OH- in CH 2Cl2 solution; neutral and anionic structures of 1-Pt were characterized by single crystal X-ray diffraction analysis..
40. Yong Shu Xie, Keisuke Yamaguchi, Motoki Toganoh, Hidemitsu Uno, Masaaki Suzuki, Shigeki Mori, Shohei Saito, Atsuhiro Osuka, Hiroyuki Furuta, Triply N-confused hexaphyrins
Near-infrared luminescent dyes with a triangular shape, Angewandte Chemie - International Edition, 10.1002/anie.200900596, 48, 30, 5496-5499, 2009.07, Getting in shape: Meso-pentafluorophenyl triply N-confused hexaphyrins have been synthesized in the free-base and oxidized forms and shown to have a triangular shape and efficient emission in the NIR region (see picture). The triangular shape is achieved by the presence of alternating confused and normal pyrrole rings. DFT calculations show that the triangular shape is more stable than a rectangular form..
41. Yoshiya Ikawa, Hiroyuki Harada, Motoki Toganoh, Hiroyuki Furuta, Synthesis and protonation behavior of a water-soluble N-fused porphyrin
Conjugation with an oligoarginine by click chemistry, Bioorganic and Medicinal Chemistry Letters, 10.1016/j.bmcl.2009.03.066, 19, 9, 2448-2452, 2009.05, A water-soluble derivative of N-fused porphyrin (NFP) possessing a nona-arginine (R9) peptide tail was synthesized for the first time by a Cu(I)-catalyzed azide-alkyne 'click' reaction. In aqueous solution, at pH 8, the conjugated molecule (NFP-R9) exists as free base and protonated below pH < 6.5 to form monoprotonated species dominantly, and diprotonated one below pH < 2.3, while such clear two-step protonation behavior was not observed in the DMF solution..
42. Motoki Toganoh, Takayoshi Hihara, Kentaro Yonekura, Yuichi Ishikawa, Hiroyuki Furuta, Synthesis and characterization of novel azo-embedded N-confused tetraphenylporphyrin, Journal of Porphyrins and Phthalocyanines, 10.1142/S1088424609000292, 13, 2, 215-222, 2009.02, A unique class of azo porphyrin, 5,10,15,20-tetraphenyl-21-phenylazo-(2- aza-21-carbaporphyrin 1, in which an azophenyl group is embedded in N-confused porphyrin, was synthesized and characterized by 1H NMR, 13C NMR, UV-vis absorption, MS, and X-ray crystallographic analysis. Synthesis of 1 was achieved through a coupling reaction of 21-amino N-confused tetraphenylporphyrin with nitrosobenzene and subsequent deoxygenation of resulting azoxy derivative with a trioxo rhenium(VII) N-fused porphyrinato catalyst. The azo-conjugate molecule was exclusively obtained as a trans-isomer and no isomerization to the cis-isomer was observed under thermal or photoirradiation. The absorption spectrum of 1 shows a moderate red-shift due to the effective interaction between the porphyrinic π-system and the connecting azophenyl group. Upon protonation, this effect is essentially lost as a result of removing degeneracy of LUMO and LUMO+1..
43. Alagar Srinivasan, Motoki Toganoh, Teppei Niino, Atsuhiro Osuka, Hiroyuki Furuta, Synthesis of N-confused tetraphenylporphyrin rhodium complexes having versatile metal oxidation states, Inorganic chemistry, 10.1021/ic061093+, 47, 23, 11305-11313, 2008.12, A variety of N-confused tetraphenylporphyrin rhodium complexes were synthesized, and their structures and physical properties were investigated. Depending on the reaction conditions, the rhodium(I), -(III), and -(IV) complexes were produced, which exemplified the versatile coordination mode of N-confused porphyrin ligands..
44. Motoki Toganoh, Tomoyuki Kimura, Hidemitsu Uno, Hiroyuki Furuta, Doubly N-fused porphyrin, Angewandte Chemie - International Edition, 10.1002/anie.200803670, 47, 46, 8913-8916, 2008.11, (Figure Presented) Are you N-fused? Doubly N-fused porphyrin (see picture; Br red, F green, N blue) exhibits exceptionally long-wavelength absorption for an 18π aromatic system (in excess of 1600 nm). The HOMO-LUMO energy gap of doubly N-fused porphyrin is extremely small for an [18]annulenic compound and results from endocyclic extension of the porphyrin π system..
45. Motoki Toganoh, Tomoyuki Kimura, Hiroyuki Furuta, Endocyclic extension of porphyrin π-system by interior functionalization of N-confused porphyrins, Chemistry - A European Journal, 10.1002/chem.200801156, 14, 34, 10585-10594, 2008.11, Internally alkynylated or cyanated N-confused porphyrins have been prepared, and these have been characterized by NMR, UV/Vis/NIR absorption, and X-ray analysis. The desired porphyrins have been synthesized by interconversion between an N-confused porphyrin and an N-fused porphyrin. In the case of terminal alkyne derivatives, intramolecular addition of a pyrrolic NH moiety to the triple bond occurred at ambient temperature to give etheno-bridged N-confused porphyrins. Significant bathochromic shifts in the absorbances of these compounds may be reasonably explained in terms of an increase in their HOMO energy levels due to effective overlap of the porphyrin π-orbital and the bridged alkene π-orbital. The corresponding rhodium(I) complexes have also been prepared, and these have been characterized by NMR and X-ray analysis..
46. Toganoh, M.; Niino, T.; Furuta, H. , Luminescent gold(III) Organometallic Complex of N-Confused Tetraphenylporphyrin, Chem. Commun., 4070-4072, 2008.09.
47. Motoki Toganoh, Naoyuki Harada, Hiroyuki Furuta, Hydrogen-bonding network in new scorpionate-type ligand composed of pyridine/pyrrole hybrid and anion-binding behavior of the corresponding rhodium complexes in alkyne cyclotrimerization reaction, Journal of Organometallic Chemistry, 10.1016/j.jorganchem.2008.07.005, 693, 19, 3141-3150, 2008.09, New heteroscorpionate ligands (1 and 2) having a di(pyridin-2-yl)(1H-pyrrol-2-yl)methane substructure are synthesized. X-ray crystallographic analysis on 1 and 2 reveals that they form unique hydrogen bonding networks depending on the size of neighboring groups in solid states. 1 and 2 can form cationic rhodium(I) complexes, wherein the counter anions form hydrogen bondings with the pyrrolic NH moiety. In alkyne cyclotrimerization reactions using those complexes as catalyst, the catalytic activity is significantly enhanced when electron-donating counter anions is placed near the metal center..
48. Dong Hoon Won, Motoki Toganoh, Yosuke Terada, Susumu Fukatsu, Hidemitsu Uno, Hiroyuki Furuta, Near-infrared emission from bis-PtII complexes of doubly N-confused calix[6]phyrins(, Angewandte Chemie - International Edition, 10.1002/anie.200801713, 47, 29, 5438-5441, 2008.07, Light from confusion: A set of doubly N-confused calix[6]phyrins bearing two coordination sites (NNNC,NNNC or NNNN,NNCC) were synthesized. Their bis-PtII complexes exhibit near-infrared emission around 1000 nm, which could make these compounds ideal for biological applications. (Graph Presented)..
49. Iti Gupta, Alagar Srinivasan, Tatsuki Morimoto, Motoki Toganoh, Hiroyuki Furuta, N-confused and N-fused meso-aryl sapphyrins, Angewandte Chemie - International Edition, 10.1002/anie.200705984, 47, 24, 4563-4567, 2008.06, (Chemical Presented) A state of (con)fusion: The introduction of a confused pyrrole ring into a meso-aryl sapphyrin framework destabilizes the macrocycle and forces a fusion reaction to occur. Subsequent metalation with rhenium results in further mutation to form a domino-fused sapphyrin with a fused penta-ring system (see scheme)..
50. Tomoya Ishizuka, Shinya Ikeda, Motoki Toganoh, Ichiro Yoshida, Yuichi Ishikawa, Atsuhiro Osuka, Hiroyuki Furuta, Substitution, dimerization, metalation, and ring-opening reactions of N-fused porphyrins, Tetrahedron, 10.1016/j.tet.2008.02.041, 64, 18, 4037-4050, 2008.04, A variety of reactions such as substitution, dimerization, rhenium(I) metalation, and ring-opening reactions of N-fused porphyrin (NFP) and optical properties of the products are presented. Palladium-catalyzed cross-coupling reactions under Suzuki or Stille conditions afford aryl and arylethynyl-substituted NFPs (12, 14) and an ethynyl-bridged dimer (15) from 3-bromo-substituted NFP (3b) in 40-98% yields. Treatment of NFP with silver(I) trifluoroacetate in CHCl3 affords a dimer (22) linked at both C21-positions of the fused rings and its bis-Re(I) metal complex (24) is synthesized. X-ray structures of the 3-trifluoromethyl and 3-phenyl NFP derivatives (9e and 12a) reveal the three-center hydrogen bondings in the core. All the new NFP derivatives display unique absorption spectra, and particularly, ethyne-bridged NFP-dimer (15) shows a remarkable bathochromic shift into a near-infrared region showing an absorption band at 1020 nm with tailing up to 1100 nm. Moreover, alkoxide nucleophiles convert NFP into NCP derivatives by the cleavage of C-N bond in the fused ring, which is useful for the preparation of various C3-substituted NCPs and C21,C21′-linked NCP dimers from NFPs..
51. Motoki Toganoh, Keitaro Fujino, Shinya Ikeda, Hiroyuki Furuta, Catalytic deoxygenation of pyridine N-oxides with N-fused porphyrin rhenium complexes, Tetrahedron Letters, 10.1016/j.tetlet.2007.12.117, 49, 9, 1488-1491, 2008.02, Deoxygenation reactions of pyridine N-oxide derivatives catalyzed by N-fused porphyrin rhenium(VII) trioxo complexes are developed, affording the corresponding pyridine derivatives in quantitative yields with excellent turnover numbers up to 340,000..
52. Motoki Toganoh, Tomoyuki Kimura, Hiroyuki Furuta, Endocyclic extension of porphyrin π-system in etheno-bridged N-confused tetraphenylporphyrin, Chemical Communications, 10.1039/b713845h, 1, 102-104, 2008.01, Etheno-bridged N-confused tetraphenylporphyrin was synthesized through flipping of the confused pyrrole ring and endocyclic extension of [18]annulenic π-conjugated system was exemplified by the absorption spectra as well as the calculated Kohn-Sham orbitals..
53. Motoki Toganoh, Teppei Niino, Hiroyuki Furuta, Luminescent Au(III) organometallic complex of N-confused tetraphenylporphyrin, Chemical Communications, 10.1039/b807922f, 34, 4070-4072, 2008, An organometallic Au(iii) complex of N-confused tetraphenylporphyrin has been synthesized and its electrochemical and photophysical properties investigated; unique emission is observed in solution at ambient temperature..
54. Motoki Toganoh, Shinya Ikeda, Hiroyuki Furuta, Synthesis, reactivity, and properties of N-fused porphyrin rhenium(I) tricarbonyl complexes, Inorganic chemistry, 10.1021/ic701208g, 46, 23, 10003-10015, 2007.11, The thermal reactions of N-fused tetraarylporphyrins or N-confused tetraarylporphyrins with Re2(CO)10 gave the rhenium(I) tricarbonyl complexes bearing N-fused porhyrinato ligands (4) in moderate to good yields. The rhenium complexes 4 are characterized by mass, IR, 1H, and 13C NMR spectroscopy, and the structures of tetraphenylporphynato complex 4a and its nitro derivative 15 are determined by X-ray single crystal analysis. The rhenium complexes 4 show excellent stability against heat, light, acids, bases, and oxidants. The aromatic substitution reactions of 4 proceed without a loss of the center metal to give the nitro (15), formyl (16), benzoyl (17), and cyano derivatives (19), regioselectively. In the electrochemical measurements for 4, one reversible oxidation wave and two reversible reduction waves are observed. Their redox potentials imply narrow HOMO-LUMO band gaps of 4 and are consistent with their electronic absorption spectra, in which the absorption edges exceed 1000 nm. Theoretical study reveals that the HOMO and LUMO of the rhenium complexes are exclusively composed of the N-fused porphyrin skeleton. Protonation of 4 takes place at the 21-position regioselectively, reflecting the high coefficient of the C21 atom in the HOMO orbital. The skeletal rearrangement reaction from N-confused porphyrin Re(I) complex (8) to N-fused porphyrin Re(I) complex (4) is suggested from the mechanistic study as well as DFT calculations..
55. Motoki Toganoh, Naoyuki Harada, Tatsuki Morimoto, Hiroyuki Furuta, Experimental and theoretical studies on oligomer formation of N-confused porphyrin-zinc(II) complexes, Chemistry - A European Journal, 10.1002/chem.200600776, 13, 8, 2257-2265, 2007.06, Dimer formation of the N-confused porphyrin zinc(II), cadmium(II), and mercury(II) complexes was investigated experimentally as well as theoretically. The stable dimers were formed through coordination of the peripheral nitrogen atoms owing to flexible rotation of the confused pyrrole rings. The Z dimers were significantly more stable than the E dimers likely due to π-π interaction between the two confused pyrrole rings. The possible formation of higher oligomers such as trimers was suggested in the case of meso-unsubstituted derivatives..
56. Motoki Toganoh, Teppei Niino, Hiromitsu Maeda, Bruno Andrioletti, Hiroyuki Furuta, Unprecedented formation of a rhodium cluster triggered by rhodium-fastened N-confused gable porphyrin, Inorganic chemistry, 10.1021/ic061741p, 45, 26, 10428-10430, 2006.12, Thermal reaction of N-confused porphyrin (NCP) with [RhCl(CO) 2]2 caused unprecedented formation of tetranuclear rhodium complex Rh4(NCP)2(CO)4 having a gable-porphyrin-type structure, where two porphyrin π systems were electronically connected by the rhodium cluster..
57. Hayato Tsuji, Mikio Sasaki, Yuki Shibano, Motoki Toganoh, Takeshi Kataoka, Yasuyuki Araki, Kohei Tamao, Osamu Ito, Photoinduced electron transfer of dialkynyldisilane-linked zinc porphyrin-[60]fullerene dyad, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.79.1338, 79, 9, 1338-1346, 2006.11, A zinc porphyrin-fullerene dyad with a disilane as a σ-conjugated linker has been newly synthesized to evaluate the electron transfer ability of the oligosilane chain. Its photoinduced processes have been studied using the time-resolved fluorescence and absorption measurements. Photoexcitation of the dyad causes the energy and/or electron transfer from the excited singlet state of the ZnP to C 60 moiety in polar solvents. The charge separation takes place as a final step in the excited-state process to yield the radical-ion pair with a radical cation on the zinc porphyrin and a radical anion on the fullerene, similar to other porphyrin-fullerene dyads. Its lifetime has been estimated to be 0.43-0.52 μs on the basis of the decay rate of the fullerene radical anion in polar solvents..
58. Motoki Toganoh, Jo Konagawa, Hiroyuki Furuta, Bis[iridium(I)] complex of inverted N-confused porphyrin, Inorganic Chemistry, 10.1021/ic060203+, 45, 10, 3852-3854, 2006.05, The reaction of N-confused tetraphenylporphyrin with IrCl(CO) 2-(p-toluidine) gave a novel bis[iridium(I)] complex, wherein the confused pyrrole ring took an inverted conformation..
59. Teppei Niino, Motoki Toganoh, Bruno Andrioletti, Hiroyuki Furuta, Rhodium N-confused porphyrin-catalyzed alkene cyclopropanation, Chemical Communications, 10.1039/b608154a, 41, 4335-4337, 2006.01, Rhodium N-confused porphyrins constitute unprecedented, highly efficient tools for the cyclopropanation of styrene, affording the expected cyclopropanes in excellent yields with trans: cis ratios reaching 98: 2..
60. Toganoh, M.; Ikeda, S.; Furuta, H., Re(VII) complex of N-fused tetraphenylporphyrin, Chem. Commun., 10.1039/b508208k, 36, 4589-4591, (36): 4589-4591, 2005.10.
61. Rolfe H. Herber, Israel Nowik, Yutaka Matsuo, Motoki Toganoh, Yoichiro Kuninobu, Eiichi Nakamura, Mössbauer spectroscopy of bucky ferrocenes
Lattice dynamics and motional anisotropy of the metal atom, Inorganic chemistry, 10.1021/ic050251e, 44, 16, 5629-5635, 2005.08, Temperature-dependent 57Fe Mössbauer effect spectroscopy has been used to elucidate the metal atom dynamics in three neutral and two cationic bucky ferrocenes. For the three diamagnetic complexes Fe(C 60H5)Cp (1), Fe(C60Me5)Cp (2), and Fe(C60Ph5)Cp (3), the metal atom motion is anisotropic and the temperature dependence of the mean-square amplitude of vibration of the metal atom at a number of temperatures is reported. The Mössbauer lattice temperatures have been determined and compared to the parent ferrocene (6). The synthesis and X-ray crystal structure of 3 have been determined at 153(2) K, and the 1H and 13C NMR spectra have been recorded. The cationic complexes derived from 2 and 3 show spin-lattice relaxation. The relaxation rate appears insensitive to the nearest-neighbor environment of the metal atom in this pair..
62. Toganoh, M.; Furuta, H., Rhenium complexes of N-methyl N-confused tetraphenylporphyrin and its normal isomer, Chem. Lett., 10.1246/cl.2005.1034, 34, 7, 1034-1035, 34 (7): 1034-1035, 2005.07.
63. Toganoh, M.; Ishizuka, T.; Furuta, H., Synthesis and properties of rhenium tricarbonyl complex bearing N-fused tetraphenylporphyrin ligand, Chem. Commun., 10.1039/b406234e, 21, 2464-2465, (21): 2464-2465 , 2004.11.
64. Yoichiro Kuninobu, Yutaka Matsuo, Motoki Toganoh, Masaya Sawamura, Eiichi Nakamura, Nickel, palladium, and platinum complexes of η 5- cyclopentadienide C 60R 5 ligands. Kinetic and thermodynamic stabilization effects of the C 60Ph 5 ligand, Organometallics, 10.1021/om0499153, 23, 13, 3259-3266, 2004.06, The nickel-, palladium-, and platinum-RFC p complexes η 5-RFC p)(η 3-allylic) (3b, RFC p = C 60R 5, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η 5- RFC p)(η 3-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η 5-RFC p)(η 3-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFC p) (R = Me, Ph) and [Ni(allylic)Br] 2, [Pd(allylic)Cl] 2, or [Pt(methallyl)Cl] 2 in THF at 25 °C for 10 min. The nickel-PhFC p complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFC p complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds..
65. Motoki Toganoh, Yutaka Matsuo, Eiichi Nakamura, Synthesis of Ferrocene/Hydrofullerene Hybrid and Functionalized Bucky Ferrocenes, Journal of the American Chemical Society, 10.1021/ja037335b, 125, 46, 13974-13975, 2003.11, Hydroferration reaction of [60]fullerene or its derivative with [Fe(C5H5)(CO)2]2 gives regioselectively a ferrocene/hydrofullerene hybrid, which upon treatment with Bu4NOH and an alkyl halide affords the corresponding alkylated bucky ferrocene, again regioselectivity via an anion of the ferrocene..
66. Motoki Toganoh, Kazuhiro Suzuki, Rie Udagawa, Atsushi Hirai, Masaya Sawamura, Eiichi Nakamura, Regioselective synthesis of [60]fullerene η5-indenide R 3C60- and η5-cyclopentadienide R5C60- bearing different R groups, Organic and Biomolecular Chemistry, 10.1039/b302468g, 1, 14, 2604-2611, 2003.10, Synthesis of a symmetrical [60]fullerene indenide, unsymmetrical indenides R2R′C60- (B,C), and unsymmetical cyclopentadienides was studied. It was observed that penta-addition reactions almost always give only the penta-addition product. It was found that besides the organic products, metallic copper forms partly as a black solid and partly as a copper mirror..
67. Motoki Toganoh, Yutaka Matsuo, Eiichi Nakamura, Synthesis and catalytic activity of rhodium diene complexes bearing indenyl-type fullerene η5-ligand, Journal of Organometallic Chemistry, 10.1016/S0022-328X(03)00465-0, 683, 2, 295-300, 2003.10, Rhodium η5-complexes bearing an indenyl-type fullerene ligand, Rh[C60(PhCH2)2Ph](cod) (2), Rh[C60(PhCH2)2Ph](nbd) (3) and Rh(C70Ph3)(cod) (4), have been synthesized from the corresponding fullerene tri-adducts in 93-96% yields. X-ray crystallographic analysis of 4 indicated that the structure of 4 is similar to that of Rh(Ind)(cod). The rhodium complex 2 catalyzes alkyne trimerization reactions and hydroboration reactions..
68. Motoki Toganoh, Yutaka Matsuo, Eiichi Nakamura, Rhenium-templated regioselective polyhydrogenation reaction of [60]fullerene, Angewandte Chemie - International Edition, 10.1002/anie.200351722, 42, 30, 3530-3532, 2003.08, Functionalizing fullerenes: The first regioselective polyhydrogenation of [60]fullerene has been achieved. Upon treatment of [60]fullerene or its derivative with 9,10-dihydroanthracene in the presence of [Re 2(CO)10], transfer hydrometallation reaction takes place to give a polyhydrogenation product (see scheme). The reaction provided a pathway to a variety of metal η5 complexes of hydrofullerenes..
69. Masaya Sawamura, Yoichiro Kuninobu, Motoki Toganoh, Yutaka Matsuo, Masahiro Yamanaka, Eiichi Nakamura, Hybrid of ferrocene and fullerene, Journal of the American Chemical Society, 10.1021/ja026069j, 124, 32, 9354-9355, 2002.08, "Bucky ferrocenes", molecular hybrids of ferrocene and fullerene, have been synthesized in good yield on gram scale by treatment of C60HMe5 or C70HMe3 with [FeCp(CO)2]2 and their structures studied with physical methods including X-ray crystallography..
70. Masaya Sawamura, Noriaki Nagahama, Motoki Toganoh, Eiichi Nakamura, Regioselective penta-addition of 1-alkenyl copper reagent to [60]fullerene. Synthesis of penta-alkenyl FCp ligand, Journal of Organometallic Chemistry, 10.1016/S0022-328X(02)01305-0, 652, 1-2, 31-35, 2002.06, We have found the conditions to achieve penta-addition of an alkenyl group to [60]fullerene in good yield with the aid of an RCu-type reagent prepared from the corresponding alkenyllithium reagent. The addition took place regioselectively at the five double bonds surrounding a pentagon in the fullerene and with retention of the stereochemistry of the alkenylcopper reagent. The reaction thus produced a cyclopentadiene embedded in the fullerene core that bears five 1-alkenyl groups (1c-e)..
71. Frank E. McDonald, Fernando Bravo, Xia Wang, Xudong Wei, Motoki Toganoh, J. Ramón Rodríguez, Bao Do, Wade A. Neiwert, Kenneth I. Hardcastle, Endo-oxacyclizations of polyepoxides
Biomimetic synthesis of fused polycyclic ethers, Journal of Organic Chemistry, 10.1021/jo0110092, 67, 8, 2515-2523, 2002.04, Boron trifluoride-etherate promotes the endo-selective oxacyclization of polyepoxides derived from various acyclic terpenoid polyalkenes, including geraniol, farnesol, and geranylgeraniol, providing an efficient and stereoselective synthesis of substituted oxepanes and fused polyoxepanes. The mechanism of the oxacyclization reaction probably involves intramolecular nucleophilic addition of epoxide oxygen to open another epoxide that is activated as an electrophile by the Lewis acid. These oxacyclizations proceed stereospecifically with inversion of configuration upon opening of each epoxide to provide trans-fused polycyclic products. The oxacyclization cascade is terminated by a tethered nucleophile, which may be the carbonyl oxygen of a ketone, ester, or carbonate, or a trisubstituted alkene. The best oxacyclization yields are generally observed with tert-butyl carbonate as the terminating nucleophile, although in some cases the oxacyclization products include formation of tert-butyl ethers as a minor product. The oxacyclization transformations described herein may mimic ring-forming steps in the biosynthesis of trans-syn-trans-fused polycyclic ether marine natural products..
72. Masaya Sawamura, Motoki Toganoh, Hitoshi Iikura, Yutaka Matsuo, Atsushi Hirai, Eiichi Nakamura, Cu(i)-mediated regioselective tri-addition of Grignard reagent to [70]fullerene. Synthesis of indenyl-type metal ligand embedded into graphitic structure, Journal of Materials Chemistry, 10.1039/b202130g, 2109-2115, 2002.01, A variety of [70]fullerene derivatives bearing three organic groups C70R3H (1, R = aryl, methyl) have been synthesized in 90-99% isolated yield by the reaction of [70]fullerene with a Grignard reagent in the presence of CuBr·S(CH3)2. Deprotonation of C70R3H with a metal alkoxide gave the corresponding metal complex M(η5-C70R3)[M = K (2), Tl (3)]. X-ray crystallographic analysis as well as theoretical study revealed the nature of the 68π-electron ligand, C70R3-..
73. M. Nakamura, N. Yoshikai, M. Toganoh, E. Nakamura, [3+3] cycloaddition reaction of dipolar trimethylenemethane with active methylene compound, Synlett, SPEC. ISS, 1030-1033, 2001.06, Under mild thermal conditions, a [3+3] cycloaddition reaction between an active methylene compound and a dipolar trimethylenemethane species, which is thermally generated from 2-methylenecyclopropanone acetal, provides a dihydropyran..
74. S. Zhou, C. Burger, B. Chu, M. Sawamura, N. Nagahama, M. Toganoh, U. E. Hackler, H. Isobe, E. Nakamura, Spherical bilayer vesicles of fullerene-based surfactants in water
A laser light scattering study, Science, 10.1126/science.291.5510.1944, 291, 5510, 1944-1947, 2001.03, The low solubility of fullerenes in aqueous solution limits their applications in biology. By appropriate substitution, the fullerenes can be transformed into stabilized anions that are water soluble and can form large aggregated structures. A laser light scattering study of the association behavior of the potassium salt of pentaphenyl fullerene (Ph5C60K) in water revealed that the hydrocarbon anions Ph5C60- associate into bilayers, forming stable spherical vesicles with an average hydrodynamic radius and a radius of gyration of about 17 nanometers at a very low critical aggregation concentration of less than 10-7 moles per liter. The average aggregation number of associated particles in these large spherical vesicles is about 1.2 × 104..
75. Masaya Sawamura, Motoki Toganoh, Kazuhiro Suzuki, Atsushi Hirai, Hitoshi Iikura, Eiichi Nakamura, Stepwise synthesis of fullerene cyclopentadienide R5C60- and indenide R3C60-. An approach to fully unsymmetrically substituted derivatives, Organic Letters, 2, 13, 1919-1921, 2000.06, (Equation presented) Fullerene cyclopentadienide (PhCH2)2Ph3C60- and indenide (PhCH2)2PhC60-, each bearing two different organic groups, were efficiently synthesized through regioselective reactions of 1,4-(PhCH2)2C60 with an organocopper reagent (PhMgBr/CuBr-SMe2) or a Grignard reagent (PhMgBr) followed by deprotonation with KOtBu..
76. Masaharu Nakamura, Motoki Toganoh, Xio Qun Wang, Shigeru Yamago, Eiichi Nakamura, Intramolecular [3 + 2]cycloaddition reaction of dipolar trimethylenemethane, Chemistry Letters, 10.1246/cl.2000.664, 6, 664-665, 2000.01, A variety of alkylidenecyclopropanone acetals possessing a terminal diylophile were allowed to undergo an intramolecular [3 + 2]cycloaddition via a dipolar trimethylenemethane to obtain bicyclo[4.3.0] and [3.3.0] carbo- and heterocycles in good yields. The product selectivities were rigorously controlled by the concerted or stepwise nature of the cycloaddition reaction..
77. Masaya Sawamura, Noriaki Nagahama, Motoki Toganoh, Ulrich E. Hackler, Hiroyuki Isobe, Eiichi Nakamura, Shui Quin Zhou, Benjamin Chu, Pentaorgano[60]fullerene R5C60-. A water soluble hydrocarbon anion, Chemistry Letters, 10.1246/cl.2000.1098, 9, 1098-1099, 2000.01, A new class of hydrocarbon anions, pentaaryl- and pentamethylfullerene anions R5C60- (R = Ph, 4-BuC6H4, 4-PhC6H4, Me) was found to be stable and soluble in water. Atomic force microscopic observation and dynamic light scattering measurements indicated that the potassium salt Ph5C60K in water forms spherical aggregates with an averaged radius of about 17 nm..
78. Masaya Sawamura, Motoki Toganoh, Yoichiro Kuninobu, Seiichi Kato, Eiichi Nakamura, Synthesis of pentamethyl-monohydro[60]fullerene C60Me5H and its use as cyclopentadienyl-type ligand precursor, Chemistry Letters, 10.1246/cl.2000.270, 3, 270-271, 2000.01, Pentamethyl-monohydro[60]fullerene C60Me5H has been synthesized through five-fold addition of methyleopper reagent to C60. The anion C60Me5 generated by deprotonation of C60Me5H forms organometallic complexes with K+ and Tl+ ions with stronger metal-carbon interaction than that in the corresponding pentaphenylated ligand C60Ph5 +..
79. M. Nakamura, Motoki Toganoh, H. Ohara, E. Nakamura, Cycloaddition reactions of trimethylenemethane radical cation generated from methylenecyclopropanone thioacetal, Organic Letters, 1, 1, 7-9, 1999.07, (formula presented) A new trimethylenemethane precursor, methylenecyclopropanone thioacetal 2, was synthesized. Trimethylenemethane species generated from 2 showed broad reactivities toward electron-deficient and electron-rich olefins under thermal or photochemical conditions..