Axial Ligand Effects on the Structures of Self-Assembled Gallium–Porphyrin Monolayers on Highly Oriented Pyrolytic Graphite

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• 作者：Judith M. Kamm ; Cameron P. Iverson ; Wing-Yeung Lau ; Michael D. Hopkins
• 刊名：Langmuir
• 出版年：2016
• 出版时间：January 19, 2016
• 年：2016
• 卷：32
• 期：2
• 页码：487-495
• 全文大小：492K
• ISSN：1520-5827

文摘

Monolayers of five-coordinate gallium octaethylporphyrin complexes (Ga(OEP)X; X = Cl, Br, I, O₃SCF₃, CCPh) on highly oriented pyrolytic graphite were studied at the solid–liquid (1-phenyloctane) interface using scanning tunneling microscopy (STM) to probe the dependence of their properties on the nature of the axial X ligand. Density functional theory calculations of the gas-phase structures of the free molecules reveal that the gallium atom is positioned above the plane of the porphyrin macrocycle, with this pyramidal distortion increasing in magnitude according to X = O₃SCF₃ (displacement = 0.35 ?) < Cl, Br, I (～0.47 ?) < CCPh (0.54 ?). All compounds exhibit pseudohexagonal close-packed structures in which the porphyrin is oriented coplanar with the surface and the axial ligand is oriented perpendicular to it, and with unit-cell parameters that are within experimental error of each other (a, b = 1.34 (3)–1.39 (2) nm, Γ = 66 (2)–68 (1)°). In contrast to these close similarities, the stabilities of the monolayers are sensitive to the nature of the axial ligand: the monolayers of Ga(OEP)(O₃SCF₃) and Ga(OEP)(CCPh) exhibit damage during the STM experiment upon repeated scanning and upon toggling the sign of the bias potential, but monolayers of Ga(OEP)Cl, Ga(OEP)Br, and Ga(OEP)I do not. A second important ligand-influenced property is that Ga(OEP)I forms bilayer structures, whereas the other Ga(OEP)X compounds form monolayers exclusively under identical conditions. The top layer of the Ga(OEP)I bilayer is oriented with the iodo ligand directed away from the surface, like the bottom layer, but the molecules pack in a square, lower-density geometry. The comparatively large polarizability of the iodo ligand is suggested to be important in stabilizing the bilayer structure.