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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Effect of Mutual Position of Electron Donor and Acceptor on Photoinduced Electron Transfer in Supramolecular Chlorophyll? Fullerene Dyads
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Effect of Mutual Position of Electron Donor and Acceptor on Photoinduced Electron Transfer in Supramolecular Chlorophyll? Fullerene Dyads

机译：电子供体和受体的相互位置对超分子叶绿素中光诱导电子转移的影响？富勒烯染料

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In this study we have explored the influence of mutual position of chlorin electron donor and fullerene C_(60) electron acceptor on photoinduced electron transfer. Two zinc-chlorinaza-[18]crown-6 compounds and three pyrrolidino[60]fullerenes with alkyl aminium and varying coordinative moieties were synthesized and used for self-assembling of a set of complexes via twopoint binding. The aza[18]crown6 moieties were connected to chlorins via amide linker either at 13~4 or 17~4 position, hence, being attached on different sides of the chlorin plane. Furthermore, in the former case, the linker holds the crown closely spaced, whereas, in the latter, the linker gives more space and conformational freedom for the crown with respect to the chlorin macrocycle. The coordinative moieties at fullerene site, 3-pyridine, 4-pyridine, and 3-furan, were built by utilizing the Prato reaction. The two-point binding drove the molecules into specific complex formation by self-assembling; aminium ion was chelated by crown ether, while zinc moiety of chlorin was coordinated by pyridine and furan. Such pairing resulted in distinct supramolecular chlorin-fullerene dyads with defined distance and orientation. The performed computational studies at DFT level in solution, with TPSS-D3/def2-TZVP//def2-SVP, indicated different geometries and binding energies for the self-assembling complexes. Notably, the computations pointed out that for all the studied complexes, the donor?acceptor distances and binding energies were dictated by chirality of pyrrolidino ring at C_(60). The selective excitation of chlorin chromophore revealed efficient emission quenching in all dyads. The ultrafast spectroscopy studies suggested a fast and efficient photoinduced charge transfer in the dyads. The lifetimes of the charge separated states range from 55 to 187 ps in odichlorobenzene and from 14 to 60 ps in benzonitrile. Expectedly, the electron transfer rate was found to be critically dependent on the donor?acceptor distance; additionally, the mutual orientation of these entities was found to have significant contribution on the rate.
机译：在这项研究中，我们探索了二氢卟酚电子供体和富勒烯C_（60）电子受体的相互位置对光诱导电子转移的影响。合成了两个锌-绿藻基-[18] crown-6化合物和三个具有烷基铝和不同配位基团的吡咯烷基[60]富勒烯，并通过两点结合将其用于自组装。 aza [18] crown6部分通过酰胺连接基在13〜4或17〜4位置与二氢卟酚连接，因此分别连接在二氢卟酚平面的两侧。此外，在前一种情况下，接头保持冠紧密间隔，而在后者的情况下，接头相对于二氢卟酚大环为冠提供了更大的空间和构象自由度。利用普拉托反应，在富勒烯位点的配位基团3-吡啶，4-吡啶和3-呋喃被构建。两点结合使分子通过自组装而形成特定的复合物。铵离子被冠醚螯合，而二氢卟酚的锌部分被吡啶和呋喃配位。这种配对导致具有确定的距离和方向的不同的超分子二氢卟啉-富勒烯二元组。在溶液中使用TPSS-D3 / def2-TZVP // def2-SVP进行的DFT级计算研究表明，自组装复合物具有不同的几何形状和结合能。值得注意的是，计算结果指出，对于所有研究的配合物，供体-受体的距离和结合能都是由吡咯烷基在C_（60）的手性所决定的。二氢卟酚生色团的选择性激发显示所有二联体均具有有效的发射猝灭。超快光谱学研究表明，二倍体中有快速有效的光诱导电荷转移。电荷分离态的寿命在二氯苯中为55到187 ps，在苄腈中为14到60 ps。可以预期，发现电子传输速率主要取决于施主-受主距离。此外，还发现这些实体的相互定向对速率有重大贡献。

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