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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Marcus Relationship Maintained During Ultrafast Electron Transfer Across a Supramolecular Capsular Wall
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Marcus Relationship Maintained During Ultrafast Electron Transfer Across a Supramolecular Capsular Wall

机译：在超分子囊墙上的超速电子转移期间保持Marcus关系

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摘要

Photoinduced electron transfer across an organic capsular wall between excited donors and ground-state acceptors is established to occur with rate constants varying in the range 0.32-4.0 X 10(11 )s(-1) in aqueous buffer solution. The donor is encapsulated within an anionic supramolecular capsular host, and the cationic acceptor remains closer to the donor separated by the organic frame through Coulombic attraction. Such an arrangement results in electron transfer proceeding without diffusion. Free energy of the reaction (Delta G degrees) and the rate of electron transfer show Marcus relation with inversion. From the plot, lambda and V-el were estimated to be 1.918 and 0.0058 eV, respectively. Given that the donor remains within the nonpolar solvent-free confined space, and there is not much change in the environment around the acceptor, the observed lambda is believed to be because of "internal" reorganization rather than "solvent" reorganization. A similarity exists between the capsular assembly investigated here and glass and crystals at low temperature where the medium is rigid. The estimated electronic coupling (V-el) implies the existence of interaction between the donor and the acceptor through the capsular wall. Existence of such an interaction is also suggested by H-1 NMR spectra. Results of this study suggest that molecules present within a confined space could be activated from outside. This provides an opportunity to probe the reactivity and dynamics of radical ions within an organic capsule.
机译：建立在激发供体和地态受体之间的有机囊壁穿过有机囊壁的光导电，以在水性缓冲溶液中的0.32-4.0×10（11）℃（-1）范围内变化的速率常数。供体包封在阴离子超分子囊孔中，阳离子受体通过库仑吸引力更接近由有机框架分离的供体。这种布置导致电子转移进行而不扩散。反应的自由能（Delta G度）和电子转移速率显示与反转的Marcus关系。从绘图，λ和v-el估计分别为1.918和0.0058eV。鉴于供体仍然在非极性溶剂的狭窄空间内，受体周围的环境中没有太大变化，所观察到的λ是因为“内部”重组而不是“溶剂”重组。在这里研究的囊组件和低温下的玻璃和晶体之间存在相似性存在于介质刚性的低温下。估计的电子耦合（V-EL）意味着通过囊壁与受体之间的相互作用存在。 H-1 NMR光谱还提出了这种相互作用的存在。该研究的结果表明，在密闭空间内存在的分子可以从外部激活。这提供了探讨有机胶囊内自由基离子的反应性和动态的机会。

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