Order−Disorder Transitions in Self-Assembled Monolayers: A 13C Solid-State NMR Study

The effect of the chain length and temperature on ordering of alkylphosphonate, (C n H 2 n +1 )PO 3 H 2, n = 8−18, monolayers on ZrO 2 was characterized by solid-state 13 C NMR. Alkylphosphonate monolayers with chain lengths of n < 16 are disordered at room temperature. C 18 monolayers of thiols and phosphonates both show reversible chain melting at ∼50 °C. This chain length dependence, as well as variable-temperature spectra, demonstrates that the thermal stabilities of conformational order in phosphonate and thiol monolayers are similar. In general, the initial free volume in a self-assembled monolayer on a rough surface is large enough to allow reversible thermal disordering although the headgroup remains rigid.