The adsorption of 1,4-phenylene diisocyanide (PDI) is studied on gold films as a function of PDI exposure from benzene solution by a combination of attenuated total internal reflection infrared (ATR-IR) spectroscopy and conductivity measurements. The infrared spectrum found for low PDI doses exhibits a single isocyanide vibrational peak consistent with the formation of -(Au-PDI)- oligomer chains that have been identified previously on a Au(111) surface dosed in ultrahigh vacuum. Larger solution doses cause the isocyanide peaks to split into two, with the lower-frequency vibrations corresponding to a free isocyanide mode, indicating the formation of a perpendicular, vertically bonded PDI molecule. This observation also rationalizes the apparent disparity between studies of the chemistry of PDI on gold in ultrahigh vacuum and with solution dosing. Since it has been shown previously that the -(Au-PDI)- oligomer chains are capable of providing conductive linkages between gold nanoparticles on an insulating mica substrate, it was proposed that higher PDI doses from solution should cause a decrease in conductivity due to chain disruption. This effect was found experimentally, thereby providing corroborative evidence for the above conclusions. (C) 2016 Elsevier B.V. All rights reserved.
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ABELES B, 1975, ADV PHYS, V24, P407, DOI 10.1080/00018737500101431
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Iowa State Univ, US DOE, Ames Lab, Ames, IA 50011 USA
Iowa State Univ, Dept Chem, Ames, IA 50011 USAIowa State Univ, US DOE, Ames Lab, Ames, IA 50011 USA
Angelici, Robert J.
Lazar, Mihaela
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Isotop & Mol Technol, Natl Inst Res & Dev, Cluj Napoca 400293, RomaniaIowa State Univ, US DOE, Ames Lab, Ames, IA 50011 USA
机构:
Iowa State Univ, US DOE, Ames Lab, Ames, IA 50011 USA
Iowa State Univ, Dept Chem, Ames, IA 50011 USAIowa State Univ, US DOE, Ames Lab, Ames, IA 50011 USA
Angelici, Robert J.
Lazar, Mihaela
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Isotop & Mol Technol, Natl Inst Res & Dev, Cluj Napoca 400293, RomaniaIowa State Univ, US DOE, Ames Lab, Ames, IA 50011 USA