The Hammett equation is commonly used to theoretically depict the remote electronic effects of substituents on catalytic activities of metal nodes of metal-organic frameworks (MOFs). However, the application of the theory to MOF catalysts usually encounters problems because it relies heavily on empirical parameters with unknown transferability. To develop an alternative prediction theory, the linker orbital energy model has been proposed by density functional theory calculations. The model provides a simple method to approximately depict the remote electronic substituent effects on catalytic activities of metal nodes of MOFs, and its general applicability to MOFs is supported by extensively revisiting the structure-activity relationships reported in the literatures. The model can be used to design catalytic activity of metal nodes of MOFs by engineering the electronic properties of linkers and substituents.

Hammett 方程通常用于从理论上描述取代基对金属有机骨架 (MOF) 金属节点催化活性的远程电子效应。然而，该理论在 MOF 催化剂上的应用通常会遇到问题，因为它严重依赖于可转移性未知的经验参数。为了发展替代预测理论，已经通过密度泛函理论计算提出了连接子轨道能量模型。该模型提供了一种简单的方法来近似描述远程电子取代基对 MOF 金属节点催化活性的影响，其对 MOF 的普遍适用性得到了广泛重新审视文献中报道的结构-活性关系的支持。