Bidirectional Electron Transfer Capability in Phthalocyanine-Sc3N@I(h)-C80 Complexes.
Bidirectional Electron Transfer Capability in Phthalocyanine-Sc3N@I(h)-C80 Complexes.
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DOI：
10.1021/jacs.5b06454
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发表时间：
2015-10
影响因子：
15
通讯作者：
O. Trukhina;M. Rudolf;G. Bottari;T. Akasaka;L. Echegoyen;T. Torres;D. Guldi
中科院分区：
文献类型：
--
作者：
O. Trukhina;M. Rudolf;G. Bottari;T. Akasaka;L. Echegoyen;T. Torres;D. Guldi
为了激活氧化和/或还原电子转移反应，已经制备了N-吡啶基取代的Sc3N@I（h）-C80（4）和C60（3）富勒烯吡咯烷，并通过锌-吡啶基、金属-配体配位轴向配位到富电子（1）或缺电子（2）Zn（II）酞菁（Zn（II）Pcs），从而提供了完整的电子给体-受体系综家族。例如，用1/4和2/4进行的一系列化学物理测定明确地表明，在前一个系综中发生Zn（II）Pc-至-Sc3N@I（h）-C80光诱导电子转移，而在后一个系综中发生Sc3N@I（h）-C80-至-Zn（II）Pc电子转移。据我们所知，这是第一次基于富勒烯的分子构建块显示出电子转移二分法，即既作为电子受体又作为电子供体，其结果仅由其对应物的电子性质决定。鉴于后者，目前的工作，其中涉及使用Sc3N@I（h）-C80，最丰富和易于纯化的内嵌金属富勒烯之一，一方面是一个范式的变化，另一方面，是一个重要的里程碑，走向建设易于制备的分子材料，具有可切换的电子转移反应性。
To activate oxidative and/or reductive electron transfer reactions, N-pyridyl-substituted Sc3N@I(h)-C80 (4) and C60 (3) fulleropyrrolidines have been prepared and axially coordinated to electron-rich (1) or electron-deficient (2) Zn(II)phthalocyanines (Zn(II)Pcs) through zinc-pyridyl, metal-ligand coordination affording a full-fledged family of electron donor-acceptor ensembles. An arsenal of photophysical assays as they were carried out with, for example, 1/4 and 2/4 show unambiguously that a Zn(II)Pc-to-Sc3N@I(h)-C80 photoinduced electron transfer takes place in the former ensemble, whereas a Sc3N@I(h)-C80-to-Zn(II)Pc electron transfer occurs in the latter ensemble. To the best of our knowledge, this is the first time that a fullerene-based molecular building block shows an electron transfer dichotomy, namely acting both as electron-acceptor or electron-donor, and its outcome is simply governed by the electronic nature of its counterpart. In light of the latter, the present work, which involves the use of Sc3N@I(h)-C80, one of the most abundant and easy-to-purify endohedral metallofullerenes, is, on one hand, a paradigmatic change and, on the other hand, an important milestone en-route toward the construction of easy-to-prepare molecular materials featuring switchable electron transfer reactivity.