Surface patterning with two-dimensional porphyrin supramolecular arrays
Surface patterning with two-dimensional porphyrin supramolecular arrays
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DOI：
10.1021/ja0531778
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发表时间：
2005-07-27
影响因子：
15
通讯作者：
Miyake, K
中科院分区：
文献类型：
--
作者：
Otsuki, J;Nagamine, E;Miyake, K
在高取向热解石墨表面制备了一系列含十八烷氧基和羧基（或吡啶基）的meso-四取代卟啉单分子层阵列。通过扫描隧道显微镜观察发现，该家族的某些卟啉化合物可以组装成不同的结构。具体地说，从5，10，15-三（4-十八烷氧基苯基）-20-（4-吡啶基）卟啉得到略微起伏的行。同时，具有更明显扭结的行由5-（4-羧基苯基）-10，15，20-三（4-十八烷氧基苯基）卟啉产生。扭结的发生取决于周围卟啉分子的排列，并由定向氢键相互作用和堆积力之间的复杂相互作用决定，包括分子-分子和分子-底物相互作用。5，10-双（4-羧基苯基）-15，20-双（4-十八烷氧基苯基）卟啉可能通过形成环状氢键而形成双层结构。这项工作证明了程序化的表面图案化的概念是可能的，通过使用卟啉结合定向分子间相互作用位点。
Monolayer arrays of a series of meso-tetra-substituted porphyrins containing octadecyloxy and carboxyl (or pyridyl) groups were prepared on the highly oriented pyrolytic graphite surface at the liquid/solid interface. It was found by means of scanning tunneling microscopy that some porphyrins from this family assemble into various patterns. Specifically, slightly undulated rows are obtained from 5,10,15-tris(4-octadecyloxyphenyl)-20-(4-pyridyl)porphyrin. Meanwhile, rows with more pronounced kinks result from 5-(4-carboxyphenyl)-10,15,20-tris(4-octadecyloxyphenyl)porphyrin. The occurrence of the kinks is dependent on the arrangement of surrounding porphyrin molecules and is determined by intricate interplay between directional hydrogen-bonding interactions and packing forces, including molecule-molecule and molecule-substrate interactions. A double-layer structure is obtained from 5,10-bis(4-carboxyphenyl)-15,20-bis(4-octadecyloxyphenyl)porphyrin, probably through cyclic hydrogen bond formation. This work proves the concept that programmed surface patterning is possible by using porphyrins incorporating directional intermolecular interaction sites.