Intermixed terpyridine-functionalized monolayers on gold: nonlinear relationship between terpyridyl density and metal ion coordination properties.

Aiming at the functionalization of surfaces with terpyridine anchors for the coordinative deposition of additional layers, mixed self-assembled monolayers (SAMs) were prepared from binary solutions of 12-(2,2′:6′,2″-terpyridine-4′-yl)dodecane-1-thiol (TDT) and 1-decanethiol (DT). The SAMs and the order of the constituting molecules were analyzed by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and time-of-flight-secondary ion mass spectrometry (ToF-SIMS). The composition of the (TDT/DT)-SAMs and with it the surface density of terpyridyl groups correlates linearly with the relative concentrations of the two compounds in the solution used for depositing them. In marked contrast, the amount of terpyridine-coordinated PdII ions significantly deviates from this trend with an optimum at a 1:3 ratio of TDT/DT. This indicates a major fraction of the terpyridines in TDT-rich SAMs not to be accessible for PdII ion coordination. In agreement, NEXAFS spectros...