Breaking the trade-off between oxidation potential and spectral response range has been an enduring challenge in the field of photocatalysis. Here, we present a general approach to initiating intra-valence band (intra-VB) hole generation in organic conjugated molecular crystals under visible light irradiation. The electron-deficient precursor with the intrinsically empty side-VB is introduced by Fe³⁺, enabling electron transition from the intra-VB to the side-VB. By studying five typical conjugated photocatalysts, we demonstrate that holes with strong oxidation potentials (up to 3.85 V vs. RHE) are generated under visible light. For PTCDA molecular crystals, the holes from the intra-VB (HOCO-1 β) couple with carbonyl groups, forming hole-coupled carbonyl sites (–C=O⁺) and extending the hole lifetime by 241 times to 84.5 ns. Efficient hole transfer from –C=O⁺ to reactants subsequently initiates oxidation reactions. The high-energy photogenerated holes exhibit scalable oxidation applicability, such as the degradation of organic pollutants in water under natural sunlight.

打破氧化电位和光谱响应范围之间的平衡一直是光催化领域的一个持久挑战。在这里，我们提出了一种在可见光照射下引发有机共轭分子晶体中价带内（VB内）空穴生成的通用方法。 Fe ³⁺引入具有本质上空的侧VB的缺电子前体，使得电子能够从VB内跃迁到VB侧。通过研究五种典型的共轭光催化剂，我们证明了在可见光下会产生具有强氧化电位（相对于 RHE 高达 3.85 V）的空穴。对于PTCDA分子晶体，来自intra-VB (HOCO-1 β)的空穴与羰基耦合，形成空穴耦合羰基位点(–C=O ⁺ )并将空穴寿命延长241倍至84.5 ns。从 –C=O ⁺到反应物的有效空穴转移随后引发氧化反应。高能光生空穴表现出可扩展的氧化适用性，例如在自然阳光下降解水中的有机污染物。