2007 Fiscal Year Final Research Report Summary
Synthesis and Function of Crystalline-state Photoresponsive Metal Complexes with Active S-S Bond
| Project/Area Number |
16350029
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Kanazawa University |
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Principal Investigator |
ISOBE Kiyoshi Kanazawa University, Graduate School of Natural Science and Technology, Professor (70101285)
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| Co-Investigator(Kenkyū-buntansha) |
HAYASHI Yoshihito Kanazawa University, Graduate School of Natural Science and Technology, Associate Professor (10231531)
NAKAI Hidetaka Kanazawa University, Graduate School of Natural Science and Technology, Assistant Professor (70377399)
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| Project Period (FY) |
2004 – 2007
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| Keywords | Active S-S Bond / Crystalline-state Reaction / Photoresponsive Function / Photochromism / Variable Temperature Solid State ^2H NMR Spectroscopy / Chiral Crystalzation / Absolute Asymmetric Synthesis / 光誘起相転移 |
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| Research Abstract |
In the crystalline state, the rhodium dinuclear complex[(RhCp^*)_2(μ-CH_2)_2(μ-O_2SSO_2)] (1) with a photoresponsive dithionite group (μ-O_2SSO_2) and two pentamethylcyclopentadienyl ligands (Cp^*=η^5-C_5Me_5) undergoes a 100% reversible unimolecular type T inverse photochromism upon interconversion to [(RhCp^*)_2(μ-CH_2)_2(μ-O_2SOSO)] (2). The photochromism can be followed directly by using stepwise crystal structure analysis.
In this study, we found that the photoreaction of 1 was triggered by absorption of the 510 nm light (charge transfer band from σ(S-S)to σ^*(S-S)and σ^*(Rh-Rh)orbitals assigned by DFT calculation) and included two important processes:kinetically controlled oxygen-atom transfer to produce four stereoisomers of 2 and thermodynamically controlled isomerization between the four stereoisomers of 2 to afford the most stable isomer. Although the formation rate of the four stereoisomer products was kinetically controlled and the population of the four stereoisomers produc
… More
ed in the system was thermodynamically controlled, both processes were regulated by the steric hindrance between the μ-O_2SSO_2 or μ-O_2SOSO ligand and the reaction cavity formed by the Cp^* ligands. The cooperation of both processes achieved an intriguing stereospecific oxygen-atom rearrangement to produce only one stereoisomer of 2 at the final stage of the photoreaction at room temperature.
We also determined the effect of the oxygen-atom rearrangement on the rotational motion of the two crystallographibally independent Cp^* ligands (parallel and perpendicular arrangement). Using variable-temperature ^13C CP/MAS NMR and quadrupolar echo solid-state ^2H NMR spectroscopies, before photoirradiation, the activation energies for the rotation of the parallel and perpendicular Cp^* ligands in 1 were determined to be 30±3 and 10±1 kJ/mol, respectively, and after photoirradiation, in 2, they were much lower than those in 1 (20±2 and 8±1 kJ/mol, respectively). The large decrease in the activation energy for the parallel Cp^* in 2 is attributed to the relaxation of molecular stress via a stereospecific oxygen-atom rearrangement, which suggests that the rotational motion of the Cp^* ligands is coupled to the photochromism.
Furthermore, we have found an absolute asymmetric photoisomerization of a new achiral photochromic dithionite complex having n-propyl moieties [(RhCp^<Pro>)_2(μ-CH_2)(μ-O_2SSO_2)] (Cp^<Pro>=η^5-C_5Me_4n-Propyl) in chiral crystals. This complex is crystallized in the space group of P2_12_12_1 and gives both crystals containing the helical isomers of P and M.
We performed a crystalline-state photoreaction by using these chiral crystals in similar way to [(RhCp^*)_2(μ-CH_2)(μ-O_2SSO_2)] and obtained [RhCp^<Pro>)_2(μ-CH_2)(μ-OSOSO_2)] almost quantitatively. The obtained μ-OSOSO_2 complex has an e.e value of 95%. Less
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[Journal Article] Mixed-Valence States Stabilized by Proton Transfer in a Hydrogen-Bonded Biimidazolate Rhenium Dimer2007
Author(s)
Makoto Tadokoro, Tomonori Inoue, Satoru Tamaki, Keisuke Fujii, Kazuo Isogai, Hiroshi Nakazawa, Sadamu Takeda, Kiyoshi Isobe, Nobuaki Koga, Akio Ichimura, Kazuhiro Nakasuji
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Journal Title
Angew. Chem. Int. Ed. 46
Pages: 5938-5942
Description
「研究成果報告書概要(和文)」より
Peer Reviewed
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[Journal Article] Direct Observation of Photochromic Dynamics in Crystalline-state of an Organorhodium Dithionite Complex2006
Author(s)
Hidetaka Nakai, Motohiro Mizuno, Takanori Nishioka, Nobuaki Koga, Kimie Shiomi, Yousuke Miyano, Masahiro Irie, Brian K. Breedlove, Isamu Kinoshita, Yoshihito Hayashi, Yoshiki Ozawa, Takae Yonezawa, Koshiro Toriumi, Kiyoshi Isobe
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Journal Title
Angew. Chem., Int. Ed. Eng. 45
Pages: 6473-6476
Description
「研究成果報告書概要(和文)」より
Peer Reviewed
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[Journal Article] Synthesis and Structural Characterization of a Photochromic Dirhodium Dithionite Complex : [(Cp^<ph>Rh)(μ-CH_2)(μ-O_2SSO_2)] (Cp^<Ph>=η^5-C_5Me_4Ph)2006
Author(s)
Hidetaka Nakai, Motohiro Mizuno, Takanori Nishioka, Nobuaki Koga, Kimie Shiomi, Yousuke Miyano, Masahiro Irie, Brian K. Breedlove, Isamu Kinoshita, Yoshihito Hayashi, Yoshiki Ozawa, Takae Yonezawa, Koshiro Toriumi, Kiyoshi Isobe
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Journal Title
Mol. Cryst. Liq. Cryst. 456
Pages: 63-70
Description
「研究成果報告書概要(和文)」より
Peer Reviewed
-
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[Journal Article] Mixed-Valence States Stabilized by Proton Transfer in a HydrogenBonded Biimidazolate Rhenium Dimer2006
Author(s)
Makoto Tadokoro, Tomonori Inoue, Satoru Tamaki, Keisuke Fujii, Kazuo Isogai, Hiroshi Nakazawa, Sadamu Takeda, Kiyoshi Isobe, Nobuaki Koga, Akio Ichimura, Kazuhiro Nakasuji
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Journal Title
Angew. Chem. Int. Ed. 45
Pages: 1274-1276
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Direct Observation of Photochromic Dynamics in Crystalline-state of an Organorhodium Dithionite Complex2006
Author(s)
Hidetaka Nakai, Motohiro Mizuno, Takanori Nishioka, Nobuaki Koga, Kimie Shiomi, Yousuke Miyano, Masahiro Irie, Brian K. Breedlove, Isamu Kinoshita, Yoshihito Hayashi, Yoshiki Ozawa, Takae Yonezawa, Koshiro Toriumi, Kiyoshi Isobe
-
Journal Title
Angew. Chem. Int. Ed. 45
Pages: 6473-6476
Description
「研究成果報告書概要(欧文)」より
-
[Journal Article] Synthesis and Structural Characterization of a Photochromic Dirhodium Dithionite Complex : [(Cp^<ph>Rh)(μ-CH_2)(μ-O_2SSO_2)] (Cp^<ph>=η^5-C_5Me_4Ph)2006
Author(s)
Hidetaka Nakai, Motohiro Mizuno, Takanori Nishioka, Nobuaki Koga, Kimie Shiomi, Yousuke, Miyano, Masahiro Irie, Brian K. Breedlove, Isamu Kinoshita, Yoshihito Hayashi, Yoshiki Ozawa, Takae Yonezawa, Koshiro Toriumi, Kiyoshi Isobe
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Journal Title
Mol. Cryst. Liq. Cryst. 456
Pages: 63-70
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Preparation, Crystal Structures and Spectroscopic Properties of Novel[M^<III>Cl_<3-n>(P)_<3+n>]^<n+> (M=Co, Rh ; n=0, 1, 2 or 3) Series of Complexes Containing Tripodal Tridentate Phosphine, 1, 1, 1-tris (DimeThylphosphinomethyl) ethane2005
Author(s)
Takayoshi Suzuki, Toshiaki Tsukuda, Masakazu Kiki, Sumio Kaizaki, Kiyoshi Isobe, Hideo D. Takagi, Kazuo Kashiwabara
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Journal Title
Inorg. Chim. Acta 358/8
Pages: 2501-2512
Description
「研究成果報告書概要(和文)」より
Peer Reviewed
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[Journal Article] Preparation, Crystal Structures and Spectroscopic Properties of Novel [M^<III>Cl_<3-n>(P)_<3+n>]n^+ (M = Co, Rh ; n = 0, 1, 2 or 3) Series of Complexes Containing Tripodal Tridentate Phosphine, 1,1,1-tris(Dimethylphosphinomethy1)ethane2005
Author(s)
Takayoshi Suzuki, Toshiaki Tsukuda, Masakazu Kiki, Sumio Kaizaki, Kiyoshi Isobe, Hideo D. Takagi, Kazuo Kashiwabara
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Journal Title
Inorg. Chim. Ada 358/8
Pages: 2501-2512
Description
「研究成果報告書概要(欧文)」より
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