Strong Hydrogen Bonds at the Interface between Proton-Donating and -Accepting Self-Assembled Monolayers on Au(111)
journal contributionposted on 2018-01-23, 00:00 authored by Hiroyuki S. Kato, Shinya Yoshimoto, Akira Ueda, Susumu Yamamoto, Yusuke Kanematsu, Masanori Tachikawa, Hatsumi Mori, Jun Yoshinobu, Iwao Matsuda
Hydrogen-bonding heterogeneous bilayers on substrates have been studied as a base for new functions of molecular adlayers by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRAS), and density functional theory (DFT) calculations. Here, we report the formation of the catechol-fused bis(methylthio)tetrathiafulvalene (H2Cat-BMT-TTF) adlayer hydrogen bonding with an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) on Au(111). The heterogeneous bilayer is realized by sequential two-step immersions in solutions for the individual Im-SAM and H2Cat-BMT-TTF adlayer formations. In the measurements by AFM, a grained H2Cat-BMT-TTF adlayer on Im-SAM is revealed. The coverage and the chemical states of H2Cat-BMT-TTF on Im-SAM are specified by XPS. On the vibrational spectrum measured by IRAS, the strong hydrogen bonds between H2Cat-BMT-TTF and Im-SAM are characterized by the remarkably red-shifted OH stretching mode at 3140 cm–1, which is much lower than that for hydrogen-bonding water (typically ∼3300 cm–1). The OH stretching mode frequency and the adsorption strength for the H2Cat-BMT-TTF molecule hydrogen bonding with imidazole groups are quantitatively examined on the basis of DFT calculations.
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XPSIm-SAMH 2 Cat-BMT-TTFIRASimidazole groupshydrogen-bonding waterAFMStrong Hydrogen BondsH 2 Cat-BMT-TTF adlayerimidazole-terminated alkanethiolate self-assembled monolayerH 2 Cat-BMT-TTF adlayer formationsH 2 Cat-BMT-TTF molecule hydrogenSelf-Assembled Monolayersvibrational spectrumadsorption strengthreflection absorption spectroscopyred-shifted OHadlayer hydrogenmode frequencyforce microscopyhydrogen bondsDFT calculationschemical states