RESUMEN
Conformationally rigid multipodal molecules should control the orientation and packing density of functional head groups upon self-assembly on solid supports. Common tripods frequently fail in this regard because of inhomogeneous bonding configuration and stochastic orientation. These issues are circumvented by a suitable tetrapodal diazatriptycene moiety, bearing four thiol-anchoring groups, as demonstrated in the present study. Such molecules form well-defined self-assembled monolayers (SAMs) on Au(111) substrates, whereby the tetrapodal scaffold enforces a nearly upright orientation of the terminal head group with respect to the substrate, with at least three of the four anchoring groups providing thiolate-like covalent attachment to the surface. Functionalization by condensation chemistry allows a large variety of functional head groups to be introduced to the tetrapod, paving the path toward advanced surface engineering and sensor fabrication.
RESUMEN
Studying the structure-property relations of tailored dipolar phenyl and biphenylphosphonic acids, we report self-assembled monolayers with a significant decrease in the work function (WF) of indium-tin oxide (ITO) electrodes. Whereas the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N, N-dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease in ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.