Inter‐Network Charge‐Transfer Excited State Formation Within a Two‐fold Catenated Metal–Organic Framework
Inter‐Network Charge‐Transfer Excited State Formation Within a Two‐fold Catenated Metal–Organic Framework
复制标题
两倍链状金属有机框架内的网络间电荷转移激发态形成
DOI：
10.1002/chem.202202978
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Mandal, Sukhendu
中科院分区：
文献类型：
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作者：
Nath, Akashdeep;Chawla, Sakshi;K. De, Arijit;Deria, Pravas;Mandal, Sukhendu
电荷转移激发态（CTES）定义了将光子能量分解为功产生适合于氧化还原的氧化还原当量的能力。在这里，我们报告了在两重链状结晶金属有机框架（MOF）内的网间CTES形成，该框架由两个连接体N，N′-二（4-吡啶基）-1，4，5，8-萘四羧基二酰亚胺（DPNDI）和2，6-二羧基萘（NDC）构成。结构灵活性使来自两个网的两个互补接头处于近端位置以强烈相互作用。在电化学和稳态电子光谱数据的支持下，这种基态相互作用有助于形成可以通过直接激发填充的CTES。我们绘制了持续几纳秒的CTES的动力学，并强调了这种相对长寿命的CTES的效用，如在黑暗中测量的MOF在光下的电导率增强，以及作为原理验证测试，甲基紫精在白色光下的光还原。
Charge‐transfer excited state (CTES) defines the ability to split photon energy into work producing redox equivalents suitable for photocatalysis. Here, we report inter‐net CTES formation within a two‐fold catenated crystalline metal–organic framework (MOF), constructed with two linkers, N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide (DPNDI) and 2,6‐dicarboxynaphthalene (NDC). The structural flexibility puts two complementary linkers from two nets in a proximal position to interact strongly. Supported by the electrochemical and steady‐state electronic spectroscopic data, this ground‐state interaction facilitates forming CTES that can be populated by direct excitation. We map the dynamics of the CTES which persists over a few nanoseconds and highlight the utilities of such relatively long‐lived CTES as enhanced conductivity of the MOF under light over that measured in dark and as a proof‐of‐the‐principle test, photo‐reduction of methyl viologen under white light.