Secondary Functionalization of Allyl-Terminated GaP(111)A Surfaces via Heck Cross-Coupling Metathesis, Hydrosilylation, and Electrophilic Addition of Bromine

The functionalization of single crystalline gallium phosphide (GaP) (111)A surfaces with allyl groups has been performed using a sequential chlorine-activation/Grignard reaction process. Increased hydrophobicity following reaction of a GaP(111)A surface with C3H5MgCl was observed through water contact angle measurements. Infrared spectra of GaP(111)A samples after reaction with C3H5MgCl showed the asymmetric C═C and C═C-H modes diagnostic of surface-attached allyl groups. The stability of allyl-terminated GaP(111)A surfaces under ambient and aqueous conditions was investigated. XP spectra of allyl-terminated GaP(111)A highlighted a significant resistance against interfacial oxidation both in air and in water relative to the native interface. Electrochemical impedance spectroscopy indicated a change in the flat-band potential of allyl-terminated GaP(111)A electrodes immersed in water relative to native GaP(111)A surfaces. Further, the flat-band potentials for allyl-terminated electrodes were insensitive to changes in solution pH. The utility of surface-bound allyl groups for covalent secondary functionalization of GaP(111)A interfaces was assessed through three separate reactions: Heck cross-coupling metathesis, hydrosilylation, and electrophilic addition of bromine reactions. Addition of aryl groups across the olefins on allyl-terminated GaP(111)A via Heck cross coupling was performed and confirmed through high-resolution F 1s and C 1s XP spectra and IR spectra. Control experiments with GaP(111)A surfaces functionalized with short alkanes indicated no evidence for metathesis. Hydrosilylation reactions were separately performed. Si 2s XP spectra, in conjunction with infrared spectra, similarly showed secondary evidence of surface functionalization for allyl-terminated GaP(111)A but not for CH3-terminated GaP(111)A surfaces. Similar analyses showed electrophilic addition of Br2 across the terminal olefin on an allyl-terminated GaP(111)A surface after exposure to dilute Br2 solutions in CH2Cl2. The work presented herein establishes a set of secondary reaction strategies utilizing allyl-terminated surfaces to modify chemically protected GaP surfaces.