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首页> 外文期刊>Chemistry: A European journal >Globular Dendrimers Involving a C_60 Core and a Tetraphenyl Porphyrin Funciton
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Globular Dendrimers Involving a C_60 Core and a Tetraphenyl Porphyrin Funciton

机译：涉及C_60核心和四苯基卟啉功能的球状树状聚合物

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摘要

a series of highly ocmpact globular dendrimers, 5, 21, and 22, involving a C_60 core with a T_h symmetrical addition pattern was synthesized by way of the fivefold cyclopropanation of the fullerene-porphyrin dyad 2 with dendritic malonates in the remaining octahedral positions. Whereas 5 contains classical Frechet benzyl-ether-based systems, a new type of dendra containing a flexible spacer between the branching units was developed for the synthesis of 21 and 22. The spectroscopyic, electrochemical, and photophysical properties of he tetraphenylporphyrinzinc (Zn-TPP) chromophore within the functional dendrimers depend not only on the presence but alos on the generation number of the surrounding dendra and therefore on the nanoenvironment provided by the neighboring addends. This is reflected, for example, in the bathochromic shifts of the Soret and Q-bands of the porphyrin moiety and in the shift of the first reduction potentials to more negative values for both the fullerene and porphyrin moieties with increasing generation number. Whereas in the dyad a photoinduced electron transfer from the porphyrino to the full-erene can occur, dendrimers 21 and 22 show fluorescence properties and singledt oxygen formation properties (#PHI#_(#DELTA) = 0.66 - 0.67) reminiscent to those of the parent Zn-TPP.
机译：通过富勒烯-卟啉二聚体2的五倍环丙烷化和在其余八面体位置上的树枝状丙二酸酯，合成了一系列具有C_60核心且具有T_h对称加成图案的高度紧密的球状树枝状大分子5，21和22。鉴于5包含经典的基于Frechet苄基醚的体系，因此开发了一种新型的树枝状分子，其在支化单元之间包含柔性间隔基，用于合成21和22.四苯基卟啉锌（Zn-TPP）的光谱，电化学和光物理性质功能性树状聚合物中的发色团不仅取决于存在的树突，而且还取决于周围树突的生成数，因此还取决于相邻的附加物所提供的纳米环境。例如，这反映为卟啉部分的Soret和Q带的红移和富勒烯和卟啉部分的第一还原电势向更高负值的偏移，随着世代数的增加。而在二元组中，可能发生从卟啉到富二烯的光致电子转移，而树状聚合物21和22则显示出荧光性质和单线态氧形成性质（#PHI #_（＃DELTA）= 0.66-0.67），这使人联想到。母体Zn-TPP。

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