Development of Optically Functionalized Materials based on Giant Porphyrin Arrays

基于巨型卟啉阵列的光学功能化材料的开发

• 批准号: 12440196
• 负责人: OSUKA Atsuhiro
• 金额: $ 10.18万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440196/
• 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; ポルフィリン; ポルフィリンアレー; 多量体; π電子共役; 箱形4量体; 拡張ポルフィリン; 縮環ポルフィリン; 光機能材料

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 dihedral 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 characterized, which is by far the longest man-made dicrete molecule. It is to be noted that even l-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 1500cm^<-1>.4) 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。这些双卟啉表现出系统的光谱变化后，二面角的减少。非束缚型双卟啉的两带Soret带变为四带Soret带。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。4<-1>）以5，10-二芳基金属卟啉为原料，以10-15%的产率合成了具有二维扩展π网络的共轭矩形卟啉片。

项目成果

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

Naoya Yoshida：“介观-介观连接二卟啉的首次光学解析”Tetrahedron Lett.. 41. 9287-9291 (2000)

C.-K. Min, T. Joo, M.-C. Yoon, C. M. Kim, Y. N. Hwang, D. Kim, N. Aratani, N. Yoshida, and A. Osuka: "Transient Absorption Anisotropy Study of Ultrafast Energy Transfer in Porphyrin Monomer, Its Direct meso-meso Coupled Dimer and Trimer"J. Chem. Phys.. 11

C.-K。

A. Nakano, Y. Yasuda, T. Yamazaki, S. Akimoto, I. Yamazaki, H. Miyasaka, A. Itaya, M. Murakami, and A. Osuka: "Intramolecular Energy Transfer in S_1- and S_2-states of Porphyrin Trimers"J.Phys.Chem.. 105. 4822-4833 (2001)

A. Nakano、Y. Yasuda、T. Yamazaki、S. Akimoto、I. Yamazaki、H. Miyasaka、A. Itaya、M. Murakami 和 A. Osuka：“卟啉 S_1 和 S_2 态的分子内能量转移

H.S.Cho: "Energy Transfer Processes in Phenylene-and Directly-linked Porphyrin Dimers"J.Phys.Chem.A.. 105. 4200-4210 (2001)

H.S.Cho：“亚苯基和直接连接的卟啉二聚体中的能量转移过程”J.Phys.Chem.A.. 105. 4200-4210 (2001)

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。