Long-range dynamics in the photoexcited states of rigidly linked composite molecular systems

刚性连接复合分子系统光激发态的长程动力学

• 批准号: 23550020
• 负责人: ASANO Motoko S.
• 金额: $ 3.49万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011 至 2013
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23550020/
• 关键词: 長距離相互作用; エネルギー移動; 励起状態; 不対電子; 超交換機構; リザーバー; 近赤外発光; ポルフィリン; 超交換相互作用; 長寿命化; 光エネルギー変換

Elucidation of the mechanisms for long-range dynamics is indispensable not only in understanding energy and electron transfer occurs in natural systems but also in designing systems that efficiently harvest light and generate long-lived charge-separated species. While much attention has been paid to the role of the superexchange mechanism in long-range interaction, most of studies have been carried out on linearly-linked molecular systems. In this work, we have studied, i) enhanced intersystem crossing process in a series of copper(II) porphyrin - free base porphyrin dimers linked via an aromatic spacer and ii) long-range singlet-singlet energy transfer of zinc(II) porphyrin - free base porphyrin dimers, which are linked linear or non-linear bridges. Spacer dependence of superexchange mediated excited-dynamics was discussed in rigidly linked donor-bridge-acceptor molecular systems, and it was found that molecular orbitals in the bridge part take an important role.

阐明长程动力学机制不仅对于理解自然系统中发生的能量和电子转移至关重要，而且对于设计有效收集光并产生长寿命电荷分离物质的系统也是必不可少的。 虽然超交换机制在长程相互作用中的作用受到了很多关注，但大多数研究都是在线性连接的分子系统上进行的。 在这项工作中，我们研究了，i）通过芳香族间隔基连接的一系列铜（II）卟啉-游离碱卟啉二聚体中增强的系间交叉过程，以及ii）锌（II）卟啉-游离碱卟啉二聚体的长程单线态能量转移，它们通过线性或非线性桥连接。 在刚性连接的供体-桥-受体分子系统中讨论了超交换介导的激发动力学的间隔依赖性，发现桥部分的分子轨道起着重要作用。

项目成果

Prolonged emission lifetimes of paramagnetic short lived species by reserver mechanism

通过储备机制延长顺磁短命物种的发射寿命

• 发表时间: 2013
• 作者: Motoko S. ASANO;Tomohiro OGAWA;Masanori SHIBUKI;Ken-ichi YAMASHITA;and Ken-ichi SUGIURA
• 通讯作者: and Ken-ichi SUGIURA

Prolonged emission lifetimes of paramagnetic short lived species by reserver mechanism

通过储备机制延长顺磁短命物种的发射寿命

• 发表时间: 2013
• 作者: M. S. Asano;T. Ogawa;M. Shibuki;K. Yamashita;K. Sugiura
• 通讯作者: K. Sugiura

Precise One-Pot Synthesis of End-Functionalized Conjugated Multi-Block Copolymers via Combined Olefin Metathesis and Wittig-type Coupling

• DOI: 10.1021/ma4022554
• 发表时间: 2013-12
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: K. Nomura;Tahmina Haque;Taira Onuma;Fatin Hajjaj;M. Asano;A. Inagaki

Superexchange Mediated Energy Transfer in m- and p-Bis(phenylethynyl) phenylene Linked Porphyrin Dimers

间-和对-双（苯乙炔基）亚苯基连接的卟啉二聚体中的超级交换介导的能量转移

• 发表时间: 2011
• 作者: Motoko S. Asano;Ken-ichi Yamashita;Ken-ichi Sugiura
• 通讯作者: Ken-ichi Sugiura

Catalyst-Free Aromatic Nucleophilic Substitution of meso-Bromoporphyrins with Azide Anion: Efficient Synthesis and Structural Analyses of meso-Azidoporphyrins

叠氮阴离子对内消旋溴卟啉的无催化剂芳香族亲核取代：内消旋叠氮卟啉的高效合成和结构分析

• DOI: 10.1021/ol202973z
• 发表时间: 2012
• 期刊: Org. Lett.
• 影响因子: 5.2
• 作者: Ken-ichi Yamashita,* Kazuuki. Kataoka;Motoko S. Asano;Ken-ichi. Sugiura*
• 通讯作者: Ken-ichi. Sugiura*