Self-Assembly Structures of a Phenol-Substituted Porphyrin in the Solid State: Hydrogen Bonding, Kagomé Lattice, and Defect Tolerance

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• 作者：Jonathan P. Hill ; Yutaka Wakayama ; Misaho Akada ; Katsuhiko Ariga
• 刊名：Journal of Physical Chemistry C
• 出版年：2007
• 出版时间：November 8, 2007
• 年：2007
• 卷：111
• 期：44
• 页码：16174 - 16180
• 全文大小：1488K
• 年卷期：v.111,no.44(November 8, 2007)
• ISSN：1932-7455

文摘

The X-ray crystal structure and surface-adsorbed self-assembled structures of the porphyrin 5,10,15,20-tetrakis(3,5-dimethyl-4-hydroxyphenyl)porphyrin (1) were investigated. This compound crystallizes in thespace group P2(1)/n with a = 12.727(2) Å, b = 13.631(2) Å, c = 15.060(3) Å, = 105.720(4), and U =2514.9(7) ų. The molecules are held in a hatchlike structure with linear arrays of the molecules arrangedapproximately orthogonally under the strong influence of hydrogen-bonding interactions involving phenolicprotons and porphyrin imino nitrogen atoms. Hydrogen-bonding interactions also dictate the surface adsorbedstructures with modulation by the underlying substrate lattice [in this case, Cu(111)]. At submonolayer substratecoverage, the molecules exhibit a variety of structural motifs. There is a tendency toward the formation ofcyclic trimeric species that are surface-mobile and can act as precursors in the formation of a Kagomé 2Dporous network structure. At monolayer coverage, molecules of 1 adopt a herringbone-type structuresuperimposed on linear arrays. The molecular conformation of 1 is dictated by the substrate lattice, withmethyl groups of 1 lying at lattice vertices, giving a molecular footprint of dimensions 5l × 4l [where l is theCu(111) lattice constant].