Supramolecular Functionalization of Carbon Nano-Cluster with π-Conjugated Host Molecules

π-共轭主体分子碳纳米簇的超分子功能化

• 批准号: 13450367
• 负责人: AIDA Takuzo
• 金额: $ 7.36万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450367/
• 关键词: Fullerene; Porphyrin; π-Conjugated System; Suplamolecule; ?共役系

A methylrhodium(III) porphyrin cyclic dimer was found to form supramolecular oscillators with fullerene homo and hetero dimers such as C_<120> and C_<130>, where included fullerenes oscillate back and forth within the porphyrin dimer iso- and anisotropically, respectively, without dissociation. From thermodynamic analysis of the oscillation processes via simulation of VT-NMR spectral profiles of the complexes and saturation transfer experiments, these oscillations are found to be entropy-driven and retarded by the solvent-fullerene interactions.From SQUID and 2D-ESR measurements, ferromagnetic coupling of spins between paramagnetic copper porphyrin cyclic dimers and La@C_<82> was found upon complextaion of the host and guest molecules, while the dimer alone or with diamagnetic C_<60> does not show any interaction of the spins at the host molecules.

发现甲基铑卟啉环状二聚体与富勒烯均聚体和杂二聚体如C_和C_形成超分子振荡器<120><130>，其中所包含的富勒烯分别在卟啉二聚体中等向和各向异性地来回振荡，而不解离。通过VT-NMR光谱模拟和饱和转移实验对振荡过程进行了热力学分析，发现这些振荡是由熵驱动的，并受到溶剂-富勒烯相互作用的阻碍.通过SQUID和2D-ESR测量，发现顺磁性铜卟啉环状二聚体与La@C_<82>在主客体分子络合时存在铁磁自旋耦合，而二聚体单独或与反磁性C_在<60>主体分子上不存在任何自旋相互作用.

项目成果

J.Y.Zheng, K.Tashiro, Y.Hirabayashi, K.Kinbara, K.Saigo, T.Aida, S.Sakamoto, K.Yamaguchi: "Cyclic Dimers of Metalloporphyrins as Tunable Hosts for Fullerenes : A Remarkable Effect of Rh(III)"Angewandte Chemie International Edition. 40・10. 1857-1861 (2001)

J.Y.Zheng、K.Tashiro、Y.Hirabayashi、K.Kinbara、K.Saigo、T.Aida、S.Sakamoto、K.Yamaguchi：“金属卟啉环状二聚体作为富勒烯的可调宿主：Rh(III) 的显着效应《Angewandte Chemie 国际版》。40・10。1857-1861 (2001)

K.Tashiro, Y.Hirabayashi, T.Aida, K.Saigo, K.Fujiwara, K.Komatsu, S.Sakamoto, K.Yamaguchi: "A Supramolecular Oscillator Composed of Carbon Nanocluster C_<120> and a Rhodium(III) Porphyrin Cyclic Dimer"Journal of American Chemical Society. 124. 12086-12087

K.Tashiro、Y.Hirabayashi、T.Aida、K.Saigo、K.Fujiwara、K.Komatsu、S.Sakamoto、K.Yamaguchi：“由碳纳米簇 C_<120> 和铑 (III) 组成的超分子振荡器

J.-Y. Xheng, K. Tashiro, Y. Hirabayashi, K. Kinbara, K. Saigo, T. Aida, S. Sakamoto, K. Yamaguchi: "Cyclic Dimers of Metalloporphyrins as Tunable Hosts for Fullerenes : A Remarkable Effect of Rh (III)"Angewandte Chemie International Edition. 40(10). 1857-

J.-Y。

J.-Y.Fheny, K.Tashiro, Y.Hirabayashi, K.Kinhira K.Saigo, T.Aida, S.Sakamoto, K.Yamaguchi: "Cyclic Dimers of Metalloporphyrins as Tunable Hesta for Fullerens, ARemarkable Effect of Rhodium(III)"Augewandee Chemie International Edition. 40(10). 1857-1861 (20

J.-Y.Fheny、K.Tashiro、Y.Hirabayashi、K.Kinhira K.Saigo、T.Aida、S.Sakamoto、K.Yamaguchi：“金属卟啉环状二聚体作为富勒烯的可调节 Hesta，铑的显着效果（

K.Tashiro, Y.Hirabayashi, Y.Aida, K.Saigo, K.Fujiwara, K.Komatsu, S.Sakamoto, K.Yamaguchi: "A Supramolecular Oscillator Composed of Dumbbell-Shaped Carbon Nanocluster C120 and a Rhodium(III) Porphyrin Cyclic Dimer"Journal of American Chemical Society. 124

K.Tashiro、Y.Hirabayashi、Y.Aida、K.Saigo、K.Fujiwara、K.Komatsu、S.Sakamoto、K.Yamaguchi：“由哑铃形碳纳米簇 C120 和铑 (III) 组成的超分子振荡器