权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Development of Supramolecular Photocatalytic Systems

超分子光催化系统的发展

基本信息

批准号：
16205020
负责人：
FUKUZUMI Shunichi
金额：
$ 31.2万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

Longer lifetimes of the charge-separated (CS) state than that of the natural photosynthetic reaction center have been achieved by using suitable chromophores and redox components, namely zinc porphyrins (or zinc chlorins) and fullerenes, which are linked with covalent bonds. A remarkably long lived electron-transfer state as compared with the natural photosynthetic reaction center has also been attained by using a simple donor-acceptor dyad, 9-mesityl-10-methylacridinium ion. However, construction of artificial photosynthetic model systems containing multiple photosynthetic reaction centers has remained as a great challenge because of the synthetic difficulty. We have developed multiple photosynthetic reaction centers composed of light-harvesting multi-porphyrin units and charge-separation units, which have been combined by non-covalent bonds such as π-π-interaction and coordination to attain long-lived CS states. First, multi-porphyrin systems were developed using porphyrin dendrimers … More and porphyrin-peptide oligomers. Then, they are combined with the reaction center units with electron acceptors by non-covalent bonds. For example, a π-extended viologen derivative can form a supramolecular complex with free base porphyrin dendrimers. The energy migration occurs efficiently among the porphyrin units, followed by efficient electron transfer. The lifetime of CS state becomes longer with increasing generation of porphyrin dendrimer. This indicates that the CS lifetime is elongated by the hole migration among porphyrin units. The longest CS lifetime was determined as 1.3 ms for the supramolecular complex of a free base porphyrin dendrimer, which contains 16 porphyrin units, with a π-extended viologen derivative in PhCN at 298 K. Fulleropyrrolidine bearing a pyridine coordinating ligand (C_<60>py) or imidazole ligand (C_<60>Im) also forms supramolecular complexes with zinc porphyrin dendrimers and zinc porphyrin-peptide oligomers. The CS states of the supramolecular complexes were detected as the transient absorption spectra by laser flash photolysis measurements. The longest CS lifetime was attained as 1.7 ms for the supramolecular complex of a zinc porphyrin-peptide hexadecamer, which contains 16 porphyrin units, with C_<60>py in benzonitrile (PhCN) at 298 K. The organization of such porphyrin and fullerene molecules has been applied to construct efficient light energy conversion systems such as photovoltaic devices. Less

通过使用合适的发色团和氧化还原成分，即通过共价键连接的锌卟啉（或锌二氢卟酚）和富勒烯，可以实现比天然光合反应中心更长的电荷分离（CS）态寿命。通过使用简单的供体-受体二元体9-异三甲苯基-10-甲基吖啶鎓离子，还获得了与天然光合反应中心相比寿命非常长的电子转移状态。然而，由于合成困难，构建包含多个光合反应中心的人工光合模型系统仍然是一个巨大的挑战。我们开发了由光捕获多卟啉单元和电荷分离单元组成的多个光合反应中心，它们通过π-π相互作用和配位等非共价键结合以获得长寿命的CS态。首先，使用卟啉树枝状聚合物和卟啉肽低聚物开发了多卟啉系统。然后，它们通过非共价键与带有电子受体的反应中心单元结合。例如，π-延伸的紫精衍生物可以与游离碱卟啉树枝状聚合物形成超分子复合物。能量迁移在卟啉单元之间有效地发生，随后是有效的电子转移。随着卟啉树枝状聚合物生成的增加，CS态的寿命变得更长。这表明，卟啉单元之间的空穴迁移延长了CS寿命。游离碱卟啉树枝状聚合物的超分子复合物的最长 CS 寿命测定为 1.3 ms，该游离碱树枝状聚合物包含 16 个卟啉单元，在 298 K 的 PhCN 中具有 π 延伸的紫精衍生物。带有吡啶配位配体 (C_ 60 > py) 或咪唑配体 (C_ 60 > Im) 的富勒吡咯烷还与锌卟啉树枝状聚合物和锌卟啉肽低聚物形成超分子复合物。通过激光闪光光解测量，将超分子复合物的 CS 态检测为瞬态吸收光谱。锌卟啉-肽十六聚体的超分子复合物包含16个卟啉单元，在苯甲腈(PhCN)中的C_60py在298K下获得了最长的CS寿命，为1.7ms。这种卟啉和富勒烯分子的组织已被应用于构建高效的光能转换系统，例如光伏器件。较少的