Synthesis of linear-shaped rhenium bipyridine polymers and their application for functional materials

• Project/Area Number: 14350451
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: 工業物理化学
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: ISHITANI Osamu Tokyo Institute of Technology, Graduate School of Science and Engineering, Associate professor, 大学院理工学研究科, 助教授 (50272282)
• Project Period (FY): 2002 – 2005
• Project Status: Completed (Fiscal Year 2005)
• Budget Amount: ¥16,900,000 (Direct Cost: ¥16,900,000); Fiscal Year 2005: ¥2,000,000 (Direct Cost: ¥2,000,000); Fiscal Year 2004: ¥3,200,000 (Direct Cost: ¥3,200,000); Fiscal Year 2003: ¥3,400,000 (Direct Cost: ¥3,400,000); Fiscal Year 2002: ¥8,300,000 (Direct Cost: ¥8,300,000)
• Keywords: rhenium multinuclear complex / phosphorous bridge ligand / energy transfer / electrochemistry / CO_2 reduction / photocatalyst / 超分子化学 / 金属錯体 / 光物性 / レニウム / 直鎖状レニウム多核錯体

Research Abstract

We successfully synthesized a new series of linear-shaped rhenium bipyridine polymers which have up to 21 Re(I) metals. A size-exclusion-chromatography with methanol and acetonitrile as eluent can be applied for isolation of the linear-shaped rhenium bipyridine polymers. This method can be also used for determination of the molecular weights of these polymers.
The Re polymers can work as photocatalyst for CO2 reduction. The photocatalytic activities of the polymers were much higher than the corresponding mononuclear Re (I) complexes. Mechanism of the photocatalytic reactions has been clarified.
We also synthesized Re(I) polymers where one-way energy transfer or concentration of photo energy occurs.
Ring-shaped Re(I) oligomers were synthesized and isolated for the first time.

Research Products

• [Journal Article] Analysis and isolation of cationic rhenium (I) and ruthenium (II) multinuclear complexes using size-exclusion chromatography (2006)
  • Author(s): H.Takeda, Y.Yamamoto, C.Nishiura, O.Ishitani
  • Journal Title: Anal. Sci. 22 Pages: 545-549
  • NAID: 10018123791
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Analysis and isolation of cationic rhenium(I) and ruthenium(II) multinuclear complexes using size-exclusion chromatography (2006)
  • Author(s): H.Takeda, Y.Yamamoto, C.Nishiura, O.Ishitani
  • Journal Title: Anal.Sci. 22 Pages: 545-549
  • NAID: 10018123791
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Photocatalytic reduction of carbon dioxide using cis,trans-[Re(dmbpy)(C0)_2(PR_3)(PR'_3)]^+ (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) (2006)
  • Author(s): H.Tsubaki, A.Sugawara, H.Takeda, B.Gholamkhass, K.Koike, O.Ishitani
  • Journal Title: Res.React.Intermed. (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Analysis and Isolation of Cationic Rhenium(I) and Ruthenium(II) Multinuclear Complexes using Size Exclusion Chromatography (2006)
  • Author(s): Hiroyuki Takeda, Youhei Yamamoto, Chiaki Nishiura, Osamu Ishitani†
  • Journal Title: Analytical Science (In press)
  • NAID: 10018123791
• [Journal Article] Effect of intramolecular π-π and CH-π interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re (bpy) (CO)_3 (PR_3)]^+ (bpy= 2, 2' -bipyridine; PR_3 = trialkyl or triarylphosphines) (2005)
  • Author(s): Tsubaki, H., Tohyama, S., Koike, K., Ishitani, O.
  • Journal Title: Dalton Trans. Pages: 385-395
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Architecture of Supramolecular Metal Complexes for Photocatalytic CO_2 Reduction : Ruthenium-Rhenium Bi- and Tetranuclear Complexes (2005)
  • Author(s): B.Gholamkhass, H.Mametsuka, K.Koike, M.Furue, O.Ishitani
  • Journal Title: Inorg. Chem. 44 Pages: 2325-2336
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Control of Photochemical, Photophysical, Electrochemical, and Photocatalytic Properties of Rhenium(I) Complexes Using Intramolecular Weak Interactions between Ligands (2005)
  • Author(s): H.Tsubaki, A.Sekine, Y.Ohashi, K.Koike, H.Takeda, H.O.Ishitani
  • Journal Title: J. Am. Chem. Soc. 127 Pages: 15544-15555
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Effect of intramolecular π-π and CH-π interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re(bpy)(CO)_3(PR_3)]^+ (bpy = 2,2'-bipyridine ; PR_3 = trialkyl or triarylphosphines) (2005)
  • Author(s): Tsubaki, H., Tohyama, S., Koike, K., Ishitani, O.
  • Journal Title: Dalton Trans. Pages: 385-395
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Architecture of Supramolecular Metal Complexes for Photocatalytic CO_2 Reduction : Ruthenium-Rhenium Bi- and Tetranuclear Complexes (2005)
  • Author(s): B.Gholamkhass, H.Mametsuka, K.Koike, M.Fume, O.Ishitani
  • Journal Title: Inorg.Chem. 44 Pages: 2326-2336
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Control of Photochemical, Photophysical, Electrochemical, and Photocatalytic Properties of Rhenium(I) Complexes Using Intramolecular Weak Interactions between Ligands (2005)
  • Author(s): H.Tsubaki, A.Sekine, Y.Ohashi, K.Koike, H.Takeda, O.Ishitani
  • Journal Title: J.Am.Chem.Soc. 127 Pages: 15544-15555
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Effect of intramolecular π-π and CH-π interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re(bpy)(CO)_3(PR_3)]^+(bpy=2,2'-bipyridine ; PR_3=trialkyl or triarylphosphines) (2005)
  • Author(s): Tsubaki, H., Tohyama, S., Koike, K., Ishitani, O.
  • Journal Title: Dalton Transactions Pages: 385-385
• [Journal Article] Architecture of Supramolecular Metal Complexes for Photocatalytic CO_2 Reduction : Ruthenium-Rhenium Bi- and Tetranuclear Complexes (2005)
  • Author(s): B.Gholamkhass, H.Mametsuka, K.Koike, M.Furue, O.Ishitani
  • Journal Title: Inorg. Chem. (印刷中)
• [Journal Article] Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)_3(PR_3)]~+ Complexes and the Properties of Their Triplet Ligand-Field Excited states (2002)
  • Author(s): K.Koike, N.Okoshi, H.Hori, K.Takeuchi, O.Ishitani, H.Tsubaki, K.Sakamoto, I.P.Clark, M.W.George, F.P.A.Johnson, J.J.Turner
  • Journal Title: J. Am. Chem. Soc. 124 Pages: 11448-11455
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)_3(PR_3)]^+ Complexes and the Properties of Their Triplet Ligand-Field Excited States (2002)
  • Author(s): K.Koike, N.Okoshi, H.Hori, K.Takeuchi, O.Ishitani, H.Tsubaki, K.Sakamoto, I.P.Clark, M.W.George, F.P.A.Johnson, J.J.Turner
  • Journal Title: J.Am.Chem.Soc. 124 Pages: 11448-11455
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Photocatalytic reduction of carbon dioxide using cis, trans- [Re(dmbpy) (CO)_2 (PR_3) (PR'_3)]^+ (dmbpy = 4, 4' -dimethyl-2, 2' -bipyridine)
  • Author(s): H.Tsubaki, A.Sugawara, H.Takeda, B.Gholamkhass, K.Koike, O.Ishitani
  • Journal Title: Res. React. Intermed. (印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] H.Tsubaki, A.Sugawara, H.Takeda, B.Gholamkhass, K.Koike, O.Ishitani: "Photocatalytic reduction of carbon dioxide using cis, trans-[Re(dmbpy)(CO)_2(PR_3)(PR'_3)]^+ (dmbpy = 4,4'-dimethyl-2,2'-bipyridine)"Research of Reaction Intermediates. (印刷中).
• [Publications] K.Koike, N.Okoshi, H.Hori, K.Takeuchi, O.Ishitani, H.Tsubaki, K.Sakamoto, I.P.Clark, M.W.George, F.P.A.Johnson, J.J.Turner: "Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)_3(PR_3)]^+ Complexes and the Properties of Their Triplet Ligand-Field Excited States"Journal of the American Chemical Society. 124. 11448-11455 (2002)