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首页> 外文期刊>Chemistry: A European journal >Supramolecular synthons on surfaces: Controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents
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Supramolecular synthons on surfaces: Controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents

机译：表面上的超分子合成子：通过氰基和烷氧基取代基的相互作用控制四芳基卟啉组装体的尺寸和周期性

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摘要

The self-assembly of three porphyrin derivatives was studied in detail on a Cu(111) substrate by means of scanning tunneling microscopy (STM). All derivatives have two 4-cyanophenyl substituents in diagonally opposed meso-positions of the porphyrin core. but differ in the nature of the other two meso-alkoxyphenyl substituents. At coverages below 0.8 monolayers, two derivatives form molecular chains, which evolve into nanoporous networks at higher coverages. The third derivative self-assembles directly into a nanoporous network without showing a one-dimensional phase. The pore-to-pore distances for the three networks depend on the size and shape of the alkoxy substituents. All observed effects are explained by 1) different steric demands of the alkoxy residues, 2) apolar (mainly dispersion) interactions between the alkoxy chains, 3) polar bonding involving both cyanophenyl and alkoxyphenyl substituents, and 4) the entropy/enthalpy balance of the network formation.
机译：通过扫描隧道显微镜（STM）在Cu（111）基板上详细研究了三种卟啉衍生物的自组装。所有衍生物在卟啉核的对角相对的中间位置具有两个4-氰基苯基取代基。但是其他两个内消旋烷氧基苯基取代基的性质不同。在覆盖率低于0.8单层时，两个衍生物形成分子链，并在覆盖率更高时演变为纳米孔网络。三阶导数直接自组装成纳米多孔网络，而不显示一维相。这三个网络的孔至孔距离取决于烷氧基取代基的大小和形状。所有观察到的影响都可以通过以下方式解释：1）烷氧基残基的空间要求不同，2）烷氧基链之间的非极性（主要是分散体）相互作用，3）涉及氰基苯基和烷氧基苯基取代基的极性键合，以及4）网络形成。

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