The surface-enhanced and tip-enhanced Raman scattering spectra of N-(6-Mercaptoacetylhexyl) quinolinium tricyanoquinodimethanides on silver coated nanosurfaces have been obtained, analyzed using Density Functional Theory Calculations, and a complete list of frequencies and assignments for the molecules are presented. The spectroscopic evidence points to the fact that monolayers of the molecule can be formed through the self-assembly process and the SERS data indicate that the monolayer attach to the silver surface through the nitrile groups. SERS spectroscopy was useful in determining the orientation of the monolayer as well as estimating its order. Deprotection the thiol group thereby terminating the tail of the molecule with a sulfur atom allowed for a selectively oriented monolayer to be formed which permanently bound the molecules to the surface preventing rearrangements. This orientation of AcSC(6)H(12)Q-3CNQ on silver a surface allowed the electron pairs of the nitrogen to be available for interaction with a second contact. Based on trigonometric tangent function calculations the tilt angle was calculated to be 38 for the protected molecule and 70 for the deprotected alkane thiol monolayer. (C) 2015 Elsevier Inc. All rights reserved.