Determination of the structure and orientation of organic molecules tethered to flat graphitic carbon by ATR-FT-IR and Raman spectroscopy

Analytical Chemistry
Franklin AnaribaRichard L McCreery

Abstract

Mono- and multilayers of nitroazobenzene (NAB), azobenzene (AB), nitrobiphenyl (NBP), biphenyl (BP), and fluorene (FL) were covalently bonded to flat pyrolyzed photoresist films (PPF) by electrochemical reduction of their diazonium derivatives. The structure and orientation of the molecular layers were probed with ATR-FT-IR and Raman spectroscopy. A hemispherical germanium ATR element used with p-polarized light at 65 degrees incidence angle yielded high signal/noise IR spectra for monolayer coverage of molecules on PPF. The IR spectra are dominated by in-plane vibrational modes in the 1000-2000-cm(-1) spectral range but also exhibit weaker out-of-plane deformations in the 650-1000-cm(-1) region. The average tilt angle with respect to the surface normal for the various molecules varied from 31.0 +/- 4.5 degrees for NAB to 44.2 +/- 5.4 degrees for FL with AB, NBP, and BP exhibiting intermediate adsorption geometries. Raman intensity ratios of NAB and AB for p- and s-polarized incident light support the conclusion that the chemisorbed molecules are in a predominantly upright orientation. The results unequivocally indicate that molecules electroreduced from their diazonium precursors are not chemisorbed flat on the PPF surface, bu...Continue Reading

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Citations

Oct 6, 2011·Langmuir : the ACS Journal of Surfaces and Colloids·Abdelaziz HoumamKallum M Koczkur
Oct 15, 2011·Nano Letters·Andrew P Bonifas, Richard L McCreery
May 28, 2011·Chemical Communications : Chem Comm·Abdelaziz HoumamDaniel F Thomas
Jun 5, 2012·Proceedings of the National Academy of Sciences of the United States of America·Sayed Y SayedAdam Johan Bergren
Jan 19, 2007·The Journal of Chemical Physics·Jing WuRichard L McCreery
Sep 21, 2006·Physical Chemistry Chemical Physics : PCCP·Alejandra RicciErnesto J Calvo
Dec 15, 2015·The Journal of Physical Chemistry Letters·Rachel Glenn, Marcos Dantus
Aug 27, 2016·Journal of the American Chemical Society·Akhtar BayatRichard L McCreery
Oct 4, 2013·Journal of the American Chemical Society·Andrey A TregubovBarbara A Messerle
Feb 6, 2014·Langmuir : the ACS Journal of Surfaces and Colloids·Sarra Gam DerouichCatherine Combellas
Mar 14, 2009·Journal of the American Chemical Society·Kristoffer MalmosKim Daasbjerg
Jun 2, 2006·Physical Chemistry Chemical Physics : PCCP·Richard L McCreeryRajendra Prasad Kalakodimi
Apr 18, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Cyril LouaultDaniel Bélanger
Jul 23, 2019·Physical Chemistry Chemical Physics : PCCP·Colin Van DyckGino A DiLabio
Dec 7, 2011·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Richard L McCreery
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Jan 1, 2018·Nanoscale Horizons : the Home for Rapid Reports of Exceptional Significance in Nanoscience and Nanotechnolgy·David D JamesRichard L McCreery
Jun 5, 2008·Langmuir : the ACS Journal of Surfaces and Colloids·Franklin AnaribaDavid F Bocian
May 15, 2008·Langmuir : the ACS Journal of Surfaces and Colloids·Paolo ActisSabine Szunerits
Mar 20, 2010·Langmuir : the ACS Journal of Surfaces and Colloids·Benjamin P Corgier, Daniel Bélanger
Apr 12, 2011·Journal of Chemical Theory and Computation·Khadga Karki, Danilo Roccatano
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Jun 19, 2008·Chemical Reviews·Richard L McCreery
Nov 28, 2006·The Journal of Physical Chemistry. B·De-en JiangSheng Dai

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