Nature‐inspired supramolecular self‐assemblies are attractive photocatalysts, but their quantum yields are limited by poor charge separation and transportation. A promising strategy for efficient charge transfer is to enhance the built‐in electric field by symmetry breaking. Herein, an unsymmetric protonation, N‐heterocyclic π‐conjugated anthrazoline‐based supramolecular photocatalyst SA‐DADK‐H+ was developed. The unsymmetric protonation breaks the initial structural symmetry of DADK, resulting in ca. 50‐fold increase in the molecular dipole, and facilitates efficient charge separation and transfer within SA‐DADK‐H+. The protonation process also creates numerous active sites for H2O adsorption, and serves as crucial proton relays, significantly improving the photocatalytic efficiency. Remarkably, SA‐DADK‐H+ exhibits an outstanding hydrogen evolution rate of 278.2 mmol g‐1 h‐1 and a remarkable apparent quantum efficiency of 25.1% at 450 nm, placing it among the state‐of‐the‐art performances in organic semiconductor photocatalysts. Furthermore, the versatility of the unsymmetric protonation approach has been successfully applied to four other photocatalysts, enhancing their photocatalytic performance by 39 to 533 times. These findings highlight the considerable potential of unsymmetric protonation induced symmetry breaking strategy in tailoring supramolecular photocatalysts for efficient solar‐to‐fuel production.

中文翻译：

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通过超分子光催化剂中的分子对称调制增强内置电场，实现高效光催化析氢

受自然启发的超分子自组装体是有吸引力的光催化剂，但它们的量子产率受到不良电荷分离和传输的限制。有效电荷转移的一种有前景的策略是通过对称性破缺来增强内置电场。在此，开发了一种不对称质子化、N-杂环π-共轭蒽唑啉基超分子光催化剂SA-DADK-H+。不对称质子化打破了 DADK 的初始结构对称性，产生了约分子偶极子增加 50 倍，促进 SA-DADK-H+ 内有效的电荷分离和转移。质子化过程还产生了许多用于H2O吸附的活性位点，并作为重要的质子中继，显着提高了光催化效率。值得注意的是，SA-DADK-H+在450 nm处表现出出色的278.2 mmol g-1 h-1的析氢速率和25.1%的显着量子效率，使其跻身有机半导体领域最先进的性能之列光催化剂。此外，不对称质子化方法的多功能性已成功应用于其他四种光催化剂，将其光催化性能提高了39至533倍。这些发现凸显了不对称质子化诱导对称性破缺策略在定制超分子光催化剂以高效生产太阳能到燃料方面的巨大潜力。