The interface bonding and orientation of a quinonoid zwitterion

Abstract

We have investigated the interaction and orientation of a strongly dipolar zwitterionic p-benzoquinonemonoimine-type molecule, with a large intrinsic dipole of 10 Debye, on both conducting and on polar insulating substrates. Specifically, we deposited (6Z)-4-(butylamino)-6-(butyliminio)-3-oxocyclohexa-1,4-dien-1-olate C₆H₂(NHR)₂(O)₂ where R = n-C₄H₉, on both gold and ferroelectric lithium niobate surfaces. An influence of both transient and static electric dipoles on the zwitterionic adsorbate has been observed. For adsorption on gold, we find that the molecule bonds to the surface through the nitrogen atoms, forming films that remain fairly uniform down to thicknesses in the 1 nm range. Adsorption of this zwitterionic compound from solution on insulating, periodically poled ferroelectric lithium niobate substrates, showed preferential adsorption on one type of ferroelectric domain. For both gold and the lithium niobate substrates, the zwitterion adopts a preferential orientation with the plane of its “C₆ core” along the surface normal. This simplified geometry of strong dipole alignment provides a symmetry simplification allowing better identification of the vibrational modes responsible for Frank-Condon scattering revealed in the fine spectroscopic signature in the photoemission spectrum.