Functionalization of [60]Fullerene and of [60]Fullerene Monoadducts by Photochemical Cycloaddition of 4‐Methyl‐1,2,4‐triazoline‐3,5‐dione.

Ulmer, Lars; Siedschlag, Christina; Mattay, Jochen

doi:10.1002/chin.200404082

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“…1 ), the ability to control the unique reactivity of triazolinediones is challenging since TAD-based ligation reactions often proceed very rapidly and are highly exergonic, even far below ambient temperature (e.g., −78 °C for reactions with cyclopentadiene) 38 , 39 . Visible light irradiation even enhances the reactivity of TADs, making them eligible to undergo [4+2]-cycloaddition reactions with fullerenes 40 , naphtalenes 41 , 42 , and even simple benzene derivatives 43 , 44 . The starting point of our light-switchable reaction manifold was to exploit the observations by Pirkle and Stickler in the 1970s, who reported the exclusive homopolymerization of 4- n -butyl-TAD ( 1 , cf.…”

Section: Resultsmentioning

confidence: 99%

Controlling thermal reactivity with different colors of light

2017

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The ability to switch between thermally and photochemically activated reaction channels with an external stimulus constitutes a key frontier within the realm of chemical reaction control. Here, we demonstrate that the reactivity of triazolinediones, powerful coupling agents in biomedical and polymer research, can be effectively modulated by an external photonic field. Specifically, we show that their visible light-induced photopolymerization leads to a quantitative photodeactivation, thereby providing a well-defined off-switch of their thermal reactivity. Based on this photodeactivation, we pioneer a reaction manifold using light as a gate to switch between a UV-induced Diels–Alder reaction with photocaged dienes and a thermal addition reaction with alkenes. Critically, the modulation of the reactivity by light is reversible and the individually addressable reaction pathways can be repeatedly accessed. Our approach thus enables a step change in photochemically controlled reactivity, not only in small molecule ligations, yet importantly in controlled surface and photoresist design.

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