Supramolecular inclusion complexes of two cyclic zinc bisporphyrins with C_(60) and C_(70): Structural, thermodynamic, and photophysical characterization

Hernández-Eguía L.P.; Escudero-Adán E.C.; Pintre I.C.; Ventura B.; Flamigni L.; Ballester P.

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Supramolecular inclusion complexes of two cyclic zinc bisporphyrins with C_(60) and C_(70): Structural, thermodynamic, and photophysical characterization

机译：具有C_（60）和C_（70）的两个环状双卟啉锌的超分子包合物：结构，热力学和光物理性质

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The formation of thermodynamically stable inclusion complexes between two cyclic zinc bisporphyrins, differing in the saturation degree of the hydrocarbon linkers that connect their porphyrin units, and the fullerenes C_(60) and C_(70) is described. Binding and photophysical studies were performed in two solvents of very different polarity: toluene and dichloromethane. UV/Vis and fluorescence titration experiments showed π-π interactions between the cyclic zinc bisporphyrins and the fullerenes. Solid-state structures were determined by X-ray diffraction analysis and gave valuable insight into the different complexation behaviors of the two macrocyclic systems towards the fullerenes. NMR titrations were also helpful in understanding the geometry of the complexes in solution. Upon fullerene complexation, the two macrocyclic bisporphyrins adopt very distinct conformations. Charge-transfer absorption bands point to ground-state interactions, and quenching of the porphyrin component luminescence indicates fast reactivity in the excited states. Energy transfer plus HOMO-HOMO and LUMO-LUMO electron-transfer processes occur within the complexes. Charge-separated states characterized by a reduced fullerene and an oxidized porphyrin radical, with lifetimes in the order of several hundred picoseconds, are detected.

机译：描述了两个环状双卟啉锌之间热力学稳定的包合配合物的形成，它们在连接它们的卟啉单元的烃连接基与富勒烯C_（60）和C_（70）的饱和度上不同。结合和光物理研究是在两种极性非常不同的溶剂中进行的：甲苯和二氯甲烷。 UV / Vis和荧光滴定实验表明，环状双卟啉锌和富勒烯之间存在π-π相互作用。固态结构通过X射线衍射分析确定，并对两个大环系统对富勒烯的不同络合行为提供了有价值的见解。 NMR滴定也有助于理解溶液中配合物的几何形状。在富勒烯络合时，两个大环双卟啉采用非常不同的构象。电荷转移吸收带指向基态相互作用，卟啉组分发光的猝灭表明在激发态下具有快速反应性。配合物中发生能量转移以及HOMO-HOMO和LUMO-LUMO电子转移过程。可以检测到以富勒烯还原和氧化卟啉自由基为特征的电荷分离状态，其寿命约为数百皮秒。

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《Chemistry: A European journal》 |2011年第51期|共14页
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Hernández-Eguía L.P.; Escudero-Adán E.C.; Pintre I.C.; Ventura B.; Flamigni L.; Ballester P.;
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正文语种 eng
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donor-acceptor systems; fullerenes; inclusion compounds; porphyrinoids; supramolecular chemistry;

机译：供体-受体体系;富勒烯;包合物;卟啉类;超分子化学;

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1. Supramolecular inclusion complexes of two cyclic zinc bisporphyrins with C_(60) and C_(70): Structural, thermodynamic, and photophysical characterization [J] . Hernández-Eguía L.P., Escudero-Adán E.C., Pintre I.C., Chemistry: A European journal . 2011,第51期

机译：具有C_（60）和C_（70）的两个环状双卟啉锌的超分子包合物：结构，热力学和光物理性质
2. Photophysical insights into supramolecular interaction of a designed bisporphyrin with fullerenes C_(60) and C_(70) [J] . Pal D., Furukawa M., Komatsu N., Spectrochimica acta, Part A. Molecular and biomolecular spectroscopy . 2011,第1期

机译：对设计的双卟啉与富勒烯C_（60）和C_（70）的超分子相互作用的光物理见解
3. Synthesis, photophysical investigations and molecular structure of the supramolecular complexes of a newly designed diporphyrin receptor with fullerenes C_(60) and C_(70) in solution [J] . Mukherjee S., Banerjee S., Bauri A.K., Journal of Molecular Structure . 2011,第1a3期

机译：新设计的双卟啉受体与富勒烯C_（60）和C_（70）的合成，光物理研究和分子结构的分子结构
4. Molecular complexes of fullerenes C_(60) and C_(70) with organic donors [C] . Rimma N. Lyubovskaya, Dmitry V. Konarev, Electrochemical Society Inc. International symposium on recent advances in the chemistry and physics of fullerenes and related materials . 1999

机译：富勒烯C_（60）和C_（70）的分子复合物与有机供体
5. Structural studies of supramolecular photochemical beta-cyclodextrin inclusion complexes. [D] . Brett, Thomas John. 1999

机译：超分子光化学β-环糊精包合物的结构研究。
6. Structural Characterization of Three Novel Hydroxamate-based Zinc Chelating Inhibitors of the C. botulinum Serotype A Neurotoxin Light Chain Metalloprotease Reveals a Compact Binding Site Resulting from 60/70 Loop Flexibility [O] . Aaron A. Thompson, Guan-Sheng Jiao, Seongjin Kim, -1

机译：所述肉毒梭菌a血清型的神经毒素轻链金属蛋白酶揭示了一个紧凑的结合位点从60/70环路灵活性所得的基于异羟肟三新锌螯合抑制剂的结构表征
7. Partial photoionization cross sections of $C_{60}$ and $C_{70}$: A gas versus adsorbed phase comparison [O] . Korica, S., Reinköster, A., Braune, M., 2010

机译：$ C_ {60} $和$ C_ {70} $的部分光电离截面：气相与吸附相的比较

Supramolecular inclusion complexes of two cyclic zinc bisporphyrins with C_(60) and C_(70): Structural, thermodynamic, and photophysical characterization

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