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首页> 外文期刊>Chemistry: A European journal >A versatile bis-porphyrin tweezer host for the assembly of noncovalent photoactive architectures: A photophysical characterization of the tweezers and their association with porphyrins and other guests
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A versatile bis-porphyrin tweezer host for the assembly of noncovalent photoactive architectures: A photophysical characterization of the tweezers and their association with porphyrins and other guests

机译：多功能双卟啉镊子主机，用于组装非共价光敏结构：镊子的光物理特征及其与卟啉和其他客人的联系

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摘要

A bis(Zn-II-porphyrin) tweezer host with anthracene components as apex and side-arms has been synthesized. Mono- (pyridine) and bidentate (4,4'-bipyridine) guests were used as models for single and double axial coordination inside the cavity, respectively. A series of dipyridylporphyrin guests with different substitution patterns and excited-state energy levels have association constants with the tweezers that are of the order of 10(6) M-1, Which is indicative of complexation with the inside of the cavity. This complexation can only occur upon an important distortion of the cavity that opens the bite by about 30%. This characteristic, in conjunction with their ability to reduce the bite distance by rotation around single bonds, makes these porphyrin tweezers amongst the most versatile so far reported, with tuning of the bite distance in the range of approximately 5-20 angstrom. Energy transfer to the free-base guest within the triporphyrin complex is nearly quantitative (95-98%) and the rates of transfer are consistent with a Forster mechanism that is characterized by a reduced orientation factor.
机译：合成了以蒽组分为顶点和侧臂的双（Zn-II-卟啉）镊子主体。单（吡啶）和双齿（4,4'-联吡啶）客体分别用作腔内单轴和双轴配位的模型。一系列具有不同取代模式和激发态能级的二吡啶基卟啉客体与镊子的缔合常数约为10（6）M-1，这表明与腔体内的络合。仅在腔体发生严重变形（使咬合张开约30％）时，才会发生这种复合。这种特性与它们通过绕单键旋转减少咬合距离的能力相结合，使得这些卟啉镊子成为迄今为止报道的最通用的镊子，其咬合距离的调节范围约为5-20埃。能量传递到三卟啉复合物中的游离碱客体几乎是定量的（95-98％），转移速率与以降低取向因子为特征的Forster机制一致。

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