Hierarchical self-assembly of cyclic dye arrays into two-dimensional honeycomb nanonetworks.
Hierarchical self-assembly of cyclic dye arrays into two-dimensional honeycomb nanonetworks.
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DOI：
10.1002/smll.200801069
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发表时间：
2008-12
期刊：
影响因子：
13.3
通讯作者：
V. Stepanenko;F. Würthner
中科院分区：
文献类型：
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作者：
V. Stepanenko;F. Würthner
环状拓扑结构的多发色团阵列对于自然光合作用中的高效捕光具有重要意义，例如紫色细菌的LH 1和LH 2复合物。[1]为了确保从LH 2到LH 1和到光合反应中心的有效能量转移，这些环状染料阵列在细菌光合膜内进一步组织成二维（2D）图案。[2]因此，在过去的十年中，大量的注意力已经投入到环状染料组件的研究中，用于开发天然系统的人工对应物。[3，4]然而，关于功能染料的2D网络的报道，回忆光合膜的结构组织是相当罕见的。[5]Chambery、Beton及其同事的一项有趣的研究表明，当母体二萘嵌苯四羧酸双酰亚胺（PBI）与三聚氰胺在高真空条件下共吸附在银/硅表面上时，形成了2D蜂窝状网络。[5a]在这篇文章中，我们报道了Zn（II）离子介导的双（三联吡啶）官能化的PBI [7]结构单元1导致环状染料阵列2的形成（图1），它在固/液界面自组织成蜂窝结构的2D纳米粒子，与光合膜中染料的结构组织有一些相似之处，螯合2，20：60，200-三联吡啶（tpy）配体已被广泛用于金属超分子化学;[8]因此，对于所需的三聚金属大环2的超分子结构，（三联吡啶基）PBI配体1是通过3-（2，20：60，200-三联吡啶-40-基）-苯胺与1，6，7，12-四氢吡啶（4-叔辛基-苯氧基）-二萘嵌苯-3，4：9，10-四羧酸二酐，分离产率为35%（参见支持信息）。双（tpy）PBI配体1与Zn（II）的配位反应
Multichromophore arrays of circular topology are of great importance for efficient light harvesting in natural photosynthesis, for example, LH1 and LH2 complexes of purple bacteria.[1] To ensure efficient energy transfer from LH2 to LH1 and to the photosynthetic reaction centers, these cyclic dye arrays are further organized into two-dimensional (2D) patterns within the bacterial photosynthetic membrane.[2] Thus, a great deal of attention has been devoted in the past decade to the investigation of cyclic dye assemblies for developing artificial counterparts of natural systems.[3, 4] However, reports on 2D networks of functional dyes that reminisce the structural organization of photosynthetic membrane are rather rare.[5] An interesting study by Champness, Beton, and co-workers revealed that 2D honeycomb networks are formed when parent perylene tetracarboxylic bisimide (PBI) is co-adsorbed with melamine on a silver/silicon surface under ultrahigh vacuum conditions.[5a] In this Communication, we report that the Zn (II)-ion-mediated self-assembly [6] of bis (terpyridine)-functionalized PBI [7] building-block 1 leads to the formation of cyclic dye array 2 (Figure 1), which self-organizes at the solid/liquid interface into honeycomb-structured 2D nanopatterns bearing some resemblance to the structural organization of dyes in the photosynthetic membrane, as revealed by atomic force microscopy (AFM).Chelating 2, 20: 60, 200-terpyridine (tpy) ligands have been widely used in metallosupramolecular chemistry;[8] thus, for the supramolecular construction of the desired trimeric metallomacrocycle 2, the angular bis (terpyridyl) PBI ligand 1 was synthesized by the condensation of 3-(2, 20: 60, 200-terpyridin-40-yl)-aniline with 1, 6, 7, 12-tetra (4-t-octyl-phenoxy)-perylene-3, 4: 9, 10-tetracarboxylic acid bisanhydride in 35% isolated yield (see Supporting Information). The complexation reaction of bis (tpy) PBI ligand 1 with Zn (II)