School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, QLD 4000, Brisbane, Australia.
Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, QLD 4000, Brisbane, Australia.
J Am Chem Soc. 2020 Dec 30;142(52):21651-21655. doi: 10.1021/jacs.0c11485. Epub 2020 Dec 18.
Herein, we introduce a comprehensive methodology to map the reactivity of photochemical systems on surfaces. The reactivity of photoreactive groups in solution often departs from their corresponding solution absorption spectra. On surfaces, the relationship between the surface absorption spectra and reactivity remains unexplored. Thus, herein, the reactivity of an -methylbenzaldehyde and a tetrazole, as ligation partners for maleimide functionalized polymers, was investigated when the reactive moieties are tethered to a surface. The ligation reaction of tetrazole functionalized surfaces was found to proceed rapidly leading to high grafting densities, while -methylbenzaldehyde functionalized substrates required longer irradiation times and resulted in lower surface coverage at the same wavelength (330 nm). Critically, wavelength resolved reactivity profiles were found to closely match the surface absorption spectra, contrary to previously reported red shifts in solution for the same chromophores.
在此，我们介绍了一种全面的方法来绘制表面上光化学反应系统的反应性。在溶液中光反应性基团的反应性往往与其相应的溶液吸收光谱不同。在表面上，表面吸收光谱与反应性之间的关系仍未得到探索。因此，在此，研究了当反应性部分连接到表面时，作为马来酰亚胺功能化聚合物的连接伙伴的 - 甲基苯甲醛和四唑的反应性。发现四唑功能化表面的连接反应迅速进行，导致高接枝密度，而 - 甲基苯甲醛功能化底物需要更长的照射时间，并且在相同波长（330nm）下导致较低的表面覆盖率。关键的是，发现波长分辨的反应性分布与表面吸收光谱非常吻合，与相同生色团在溶液中报道的红移相反。
