UV/Vis and NIR Light-Responsive Spiropyran Self-Assembled Monolayers

Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SERS), and X-ray photoelectron spectroscopies (XPS). The SAMs obtained are composed of the ring-closed form (i.e., spiropyran) only. Irradiation with UV light results in conversion of the monolayer to the merocyanine form (MC), manifested in the appearance of an N+ contribution in the N 1s region of the XPS spectrum of the SAMs, the characteristic absorption band of the MC form in the visible region at 555 nm, and the C–O stretching band in the SERS spectrum. Recovery of the initial state of the monolayer was observed both thermally and after irradiation with visible light. Several switching cycles were performed and monitored by SERS spectroscopy, demonstrating the stability of the SAMs during repeated switching between SP and MC states. A key finding in the present study is that ring-opening of the surface-immobilized spiropyrans can be induced by irradiation with continuous wave NIR (785 nm) light as well as by irradiation with UV light. We demonstrate that ring-opening by irradiation at 785 nm proceeds by a two-photon absorption pathway both in the SAMs and in the solid state. Hence, spiropyran SAMs on gold can undergo reversible photochemical switching from the SP to the MC form with both UV and NIR and the reverse reaction induced by irradiation with visible light or heating. Furthermore, the observation of NIR-induced switching with a continuous wave source holds important consequences in the study of photochromic switches on surfaces using SERS and emphasizes the importance of the use of multiple complementary techniques in characterizing photoresponsive SAMs.