Eliminating Fatigue in Surface-Bound Spiropyrans

This paper describes an experimental approach to eliminating the loss of reversibility that surface-bound spiropyrans exhibit when switched with light. Although such fatigue can be controlled in other contexts, on surfaces, the photochromic compounds are held in close proximity to each other and rel...

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Veröffentlicht in:Journal of physical chemistry. C 2019-10, Vol.123 (42), p.25908-25914
Hauptverfasser: Kumar, Sumit, Soni, Saurabh, Danowski, Wojciech, Leach, Isaac F, Faraji, Shirin, Feringa, Ben L, Rudolf, Petra, Chiechi, Ryan C
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container_end_page 25914
container_issue 42
container_start_page 25908
container_title Journal of physical chemistry. C
container_volume 123
creator Kumar, Sumit
Soni, Saurabh
Danowski, Wojciech
Leach, Isaac F
Faraji, Shirin
Feringa, Ben L
Rudolf, Petra
Chiechi, Ryan C
description This paper describes an experimental approach to eliminating the loss of reversibility that surface-bound spiropyrans exhibit when switched with light. Although such fatigue can be controlled in other contexts, on surfaces, the photochromic compounds are held in close proximity to each other and relatively few molecules modulate the properties of a device, leading to a loss of functionality after only a few switching cycles. The switching process was characterized by photoelectron spectroscopy and differences in tunneling currents in the spiropyran and merocyanine forms using eutectic Ga−In. Self-assembled monolayers comprising only the photochromic compounds degraded rapidly, while mixed monolayers with hexanethiol showed different behaviors depending on the relative humidity. Under dry conditions, no chemical degradation was observed and the switching process was reversible over at least 100 cycles. Under humid conditions, no degradation occurred, but the switching process became irreversible. The absence of degradation observed in mixed monolayers is ascribed to the lack of solvation, which increases the barrier to a key bond rotation past the available thermal energy. These results highlight important differences in the contexts in which photochromic compounds are utilized and demonstrate that they can be leveraged to extract device-relevant functionality from surface-bound switches by suppressing fatigue and irreversibility.
doi_str_mv 10.1021/acs.jpcc.9b05889
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