Donor-acceptor biomorphs from the ionic self-assembly of porphyrins.
Donor-acceptor biomorphs from the ionic self-assembly of porphyrins.
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DOI：
10.1021/ja102194x
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发表时间：
2010-05
影响因子：
15
通讯作者：
Kathleen E. Martin;Zhongchun Wang;T. Busani;Robert M. Garcia;Zhu Chen;Y. Jiang;Yujiang Song;
中科院分区：
文献类型：
--
作者：
Kathleen E. Martin;Zhongchun Wang;T. Busani;Robert M. Garcia;Zhu Chen;Y. Jiang;Yujiang Song;
通过阴离子和阳离子卟啉的自组装形成了微尺度的四叶草状结构。根据卟啉大环中络合的金属（Zn或Sn），卟啉核是电子供体或电子受体。这两种金属在阳离子四（N-乙醇-4-吡啶）卟啉和阴离子四（磺酸基苯基）卟啉中的所有四种组合导致相关的三叶草状结构，具有由X射线衍射图案指示的相似的结晶堆积。三叶草的形貌随着离子强度和自组装反应温度的增加而发生变化，但结构保持4重对称性。改变这些固体的电子和物理性质的能力（例如，通过改变卟啉中的金属）和改变卟啉亚单元之间的协同相互作用，提高了制备具有可调官能度的二元固体的可能性。例如，我们表明，来自阴离子锌卟啉（电子供体）和阳离子锡卟啉（电子受体）的三叶草是光电导体，但当金属在两个卟啉反转时，所得三叶草是绝缘体。
Microscale four-leaf clover-shaped structures are formed by self-assembly of anionic and cationic porphyrins. Depending on the metal complexed in the porphyrin macrocycle (Zn or Sn), the porphyrin cores are either electron donors or electron acceptors. All four combinations of these two metals in cationic tetra(N-ethanol-4-pyridinium)porphyrin and anionic tetra(sulfonatophenyl)porphyrin result in related cloverlike structures with similar crystalline packing indicated by X-ray diffraction patterns. The clover morphology transforms as the ionic strength and temperature of the self-assembly reaction are increased, but the structures maintain 4-fold symmetry. The ability to alter the electronic and photophysical properties of these solids (e.g., by altering the metals in the porphyrins) and to vary cooperative interactions between the porphyrin subunits raises the possibility of producing binary solids with tunable functionality. For example, we show that the clovers derived from anionic Zn porphyrins (electron donors) and cationic Sn porphyrins (electron acceptors) are photoconductors, but when the metals are reversed in the two porphyrins, the resulting clovers are insulators.