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

线形联吡啶铼聚合物的合成及其在功能材料中的应用

• 批准号: 14350451
• 负责人: ISHITANI Osamu
• 金额: $ 10.82万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14350451/
• 关键词: 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

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.

我们成功地合成了一系列新的线性联吡啶铼聚合物，它含有多达21种稀土金属。以甲醇和乙腈为洗脱液，采用粒径排除色谱法分离线状联吡啶铼聚合物。该方法也可用于测定这些聚合物的分子量。稀土聚合物可作为光催化剂用于CO2还原。聚合物的光催化活性远高于相应的单核Re (I)配合物。阐明了光催化反应的机理。我们还合成了单向能量转移或光能量集中的Re(I)聚合物。首次合成并分离了环状Re(I)低聚物。

项目成果

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)

配体之间分子内π-π和CH-π相互作用对fac-[Re(bpy)(CO)_3(PR_3)]+ (bpy = 2,2-联吡啶; PR_3 = 三烷基)结构、电化学和光谱性质的影响或三芳基膦）

• 发表时间: 2005
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: H.Tsubaki;S.Tohyama;K.Koike;O.Ishitani
• 通讯作者: O.Ishitani

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).

H.Tsubaki、A.Sukawara、H.Takeda、B.Gholamkhass、K.Koike、O.Ishitani：“利用顺式、反式-[Re(dmbpy)(CO)_2(PR_3)(PR)光催化还原二氧化碳_3)]^+ (dmbpy = 4,4-二甲基-2,2-联吡啶)“反应中间体的研究。（出版中）。

Photocatalytic reduction of carbon dioxide using cis,trans-[Re(dmbpy)(C0)_2(PR_3)(PR'_3)]^+ (dmbpy = 4,4'-dimethyl-2,2'-bipyridine)

使用 cis,trans-[Re(dmbpy)(C0)_2(PR_3)(PR_3)]^ (dmbpy = 4,4-二甲基-2,2-联吡啶)光催化还原二氧化碳

• 发表时间: 2006
• 期刊: Res.React.Intermed. (in press)
• 作者: H.Tsubaki;A.Sugawara;H.Takeda;B.Gholamkhass;K.Koike;O.Ishitani
• 通讯作者: O.Ishitani

Mechanism of the photochemical ligand substitution reactions of fac-[Re(bPY)(CO)3(PR3)]+ complexes and the properties of their triplet ligand-field excited states

• DOI: 10.1021/ja017032m
• 发表时间: 2002-09-25
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Koike, K;Okoshi, N;Turner, JJ
• 通讯作者: Turner, JJ

Analysis and isolation of cationic rhenium(I) and ruthenium(II) multinuclear complexes using size-exclusion chromatography

• DOI: 10.2116/analsci.22.545
• 发表时间: 2006-04-01
• 期刊: ANALYTICAL SCIENCES
• 影响因子: 1.6
• 作者: Takeda, H;Yamamoto, Y;Ishitani, O
• 通讯作者: Ishitani, O