Six-Coordinate Zinc Porphyrins for Template-Directed Synthesis of Spiro-Fused Nanorings.
Six-Coordinate Zinc Porphyrins for Template-Directed Synthesis of Spiro-Fused Nanorings.
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DOI：
10.1021/jacs.5b10126
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发表时间：
2015-11-18
影响因子：
15
通讯作者：
Anderson HL
中科院分区：
文献类型：
--
作者：
Favereau L;Cnossen A;Kelber JB;Gong JQ;Oetterli RM;Cremers J;Herz LM;Anderson HL
五配位构型是锌卟啉与吡啶配体的标准结合模式。在这里，我们表明，假八面体六配位锌卟啉配合物也可以在溶液中形成，利用螯合效应。UV-vis-NIR滴定表明，该第二配位的强度约为0.001。6-8 kJ mol-1。我们已经使用六配位锌卟啉配合物的形成来实现模板导向合成11个卟啉单元的3D π共轭螺稠合阵列，以非平凡拓扑结构共价连接。时间分辨荧光各向异性实验表明，电子激发离域之间的两个垂直的纳米环的螺系统的实验时间分辨率为270 fs。
Five-coordinate geometry is the standard binding mode of zinc porphyrins with pyridine ligands. Here we show that pseudo-octahedral six-coordinate zinc porphyrin complexes can also be formed in solution, by taking advantage of the chelate effect. UV–vis–NIR titrations indicate that the strength of this second coordination is ca. 6–8 kJ mol–1. We have used the formation of six-coordinate zinc porphyrin complexes to achieve the template-directed synthesis of a 3D π-conjugated spiro-fused array of 11 porphyrin units, covalently connected in a nontrivial topology. Time-resolved fluorescence anisotropy experiments show that electronic excitation delocalizes between the two perpendicular nanorings of this spiro-system within the experimental time-resolution of 270 fs.