Energy Storage upon Photochromic 6-π Photocyclization and Efficient On-Demand Heat Release with Oxidation Stimuli
Energy Storage upon Photochromic 6-π Photocyclization and Efficient On-Demand Heat Release with Oxidation Stimuli
复制标题
光致变色 6-π 光环化能量储存和氧化刺激下的高效按需放热
DOI：
10.1021/acs.jpclett.1c03052
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Kawai Tsuyoshi
中科院分区：
文献类型：
--
作者：
Asato Ryosuke;Martin Colin J.;Nakashima Takuya;Calupitan Jan Patrick;Rapenne Gwenael;Kawai Tsuyoshi
光致变色分子在两个异构体之间发生可逆的异构化反应，并伴随着热势和化学势的交换。目前的E型光致变色分子中有相当一部分被吸收的光能储存和释放，它们在紫外光激发下发生环化反应，在氧化刺激下发生反向反应。研究了8种光致变色四芳烃的闭合异构体的光致变色性质、热稳定性和级联开环反应，实验证明在单一波长η下的储能效率高达23%。它们对环化反应的高效光化学量子产率显着有助于提高储能效率，并显示出高效的级联环反反应能力。自发的环回反应被很好地抑制，因为环回反应的禁忌性质产生了足够的储热时间。
Photochromic molecules display reversible isomerization reactions between two isomers accompanied by an exchange between heat and chemical potential. A considerable part of the absorbed light energy is stored in and released from the present E-type photochromic molecules, which undergo cyclization reactions under UV light excitation and backward reactions after application of oxidative stimuli. The photochromic nature, thermal stability, and cascade ring-opening reaction of the closed form isomers of eight photochromic terarylenes are studied, and energy storage efficiencies at a single wavelength, η, as high as 23% are experimentally demonstrated. Their efficient photochemical quantum yield for the cyclization reaction markedly contributes to the high energy storage efficiency as well as showing the capability of efficient cascade cycloreversion reactions. Spontaneous cycloreversion reactions are well-suppressed because the forbidden nature of the cycloreversion reaction gives rise to sufficient heat storage duration.