Manipulating the electronic structure of organic functional materials by through-space conjugation (TSC) to achieve desirable photophysical properties has been a long-standing research focus. Although the working mechanisms of TSC have been demonstrated, the roles that the intrinsic molecular skeleton and extrinsic aggregates play remain unclear. Here four trinaphthylmethanol isomers and four trinaphthylmethane (TNM) isomers with varying connecting sites of naphthalene were synthesized, and their photophysical properties were systematically investigated. The strength of TSC was found to rise from 222-TNM to 111-TNM with the increased number of 1-naphthalene units. In particular, 111-TNM was found to support efficient long-wavelength clusteroluminescence with an absolute quantum yield of 55%. Experimental and theoretical results revealed that the inherent attribute of robust intramolecular interactions within individual molecules is fundamental for ultrastrong TSC, and intermolecular interactions play an auxiliary role in fortifying and stabilizing intramolecular interactions. This work reveals the intrinsic and extrinsic factors for manipulating TSC and provides a reliable strategy for constructing non-conjugated luminogens with efficient clusteroluminescence.

通过空间共轭 （TSC） 操纵有机功能材料的电子结构以实现理想的光物理特性一直是一个长期的研究重点。尽管已经证明了 TSC 的工作机制，但内在分子骨架和外源性聚集体所起的作用仍不清楚。在这里，合成了四种三氢乙醇异构体和四种具有不同萘连接位点的三氢甲烷 （TNM） 异构体，并系统研究了它们的光物理性质。发现 TSC 的强度从 222-TNM 上升到 111-TNM，随着 1-萘单元数量的增加。特别是，发现 111-TNM 支持高效的长波长簇发光，绝对量子产率为 55%。实验和理论结果表明，单个分子内稳健的分子内相互作用的固有属性是超强 TSC 的基础，分子间相互作用在加强和稳定分子内相互作用方面起辅助作用。这项工作揭示了操纵 TSC 的内在和外在因素，并为构建具有高效簇发光的非共轭发光物提供了一种可靠的策略。