Construction of Molecular Chain Reaction Synstem Based on Porphyrin Arreys and Chain Protochemical Reactions

基于卟啉阵列和链式原化学反应的分子链式反应体系的构建

• 批准号: 11223205
• 负责人: OSUKA Atsuhiro
• 金额: $ 22.66万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11223205/
• 关键词: porphyrin array; meso-meso linked porphyrin arrays; monodisperse giant molecule; molecular wire; porphyrin sheet; ポルフィリンシート; 励起エネルギー移動; 光合成モデル; ポルフィリン; 拡張ポルフィリン; 縮環ポルフィリン; 光機能材料; 超分子

1) We have prepared a series of meso-meso linked diporphyrins strapped with variable length dioxymethylene group. These diporphyrins exhibit systematic spectral changes upon the decrease in the dihendral angle. Two-bands shape Soret band in non-strapped diporphyrins changes into four-bands shape Soret band.2) Discrete 1024-mer of meso-meso linked porphyrin arrays has been prepared and charactrized, which is by far the longest man-made dicrete molecule. It is to be noted that even 1-240mer is certainly soluble in organic solvents and can be manipulated.3) Oxidation with Sc(OTf)_3 and DDQ realized very efficient transformation of end-phenyl capped meso-meso linked porphyrin arrays to triply-linked conjugated porphyrin arrays. The absorption spectra of these conjugated 6-mer, 8-mer and 12-mer display the electronic absorption band deep into infrared region up to 1500 cm^<-1>.Starting from 5,10-diaryl metalloporphyrin, conjugated rectangular-shaped porphyrin sheets have been prepared in 10-15% yields, which have 2-dimensionally expanded π-network.

1)我们合成了一系列带有不同长度二氧亚甲基的meso-meso连接的双卟啉。这些双卟啉在二亨德拉角减小时表现出系统的光谱变化。2）制备并表征了meso-meso连接卟啉阵列的1024-mer离散分子，这是迄今为止最长的人造离散分子。3）Sc（OTf）_3和DDQ氧化实现了端苯基封端的meso-meso连接卟啉阵列向三氟甲基连接的共轭卟啉阵列的高效转化。这些共轭的6-mer、8-mer和12-mer的吸收光谱显示电子吸收带深入到红外区直到1500 cm ~ 2<-1>。从5，10-二芳基金属卟啉出发，以10-15%的产率制备了具有二维扩展π网络的共轭矩形卟啉片。

项目成果

津田明彦: "Completely fused diporphyrins and friporphyrin"Angew.Chem.,Int.Ed.. 39・14. 2549-2552 (2000)

津田明彦：“完全融合的二卟啉和氟卟啉”Angew.Chem.，Int.Ed. 39・14（2000）。

A.Nakano: "Modified Windmill Porphyrin Arrays : Coupled Light-Harvesting and Charge Separation, Conformational Relaxation, and S_2-S_2 Energy Transfer"Chem. Eur. J.. 7. 3134-3151 (2001)

A.Nakano：“改进的风车卟啉阵列：耦合光捕获和电荷分离、构象弛豫和 S_2-S_2 能量转移”Chem。

A.Tsuda: "Fully Conjugated Porphyrin Tapes with Electronic Absorption Bands that Reach into Infrared"Science. 293. 79-83 (2001)

A.Tsuda：“具有到达红外线的电子吸收带的完全共轭卟啉带”科学。

C.-K.Min: "Transient Absorption Anisotropy Study of Ultrafast Energy Transfer in Porphyrin Monomer,Its Direct meso-meso Coupled Dimer and Trimer"J.Chem.Phys.. 114. 6750-6758 (2001)

C.-K.Min：“卟啉单体及其直接介观-介观耦合二聚体和三聚体中超快能量转移的瞬态吸收各向异性研究”J.Chem.Phys.. 114. 6750-6758 (2001)

吉田直哉: "First optical resolution of meso-meso linked diporphysins"Tetrahedron Lett.. 41. 9287-9291 (2000)

Naoya Yoshida：“介观-介观连接的二卟啉的首次光学解析”Tetrahedron Lett.. 41. 9287-9291 (2000)