The influence of mono‐ and multiple substituent effect on the reduction potential (E0) of 1,3,6‐triphenyl fulvenes is investigated using B3LYP‐SMD/6‐311+G(d,p) level density functional theory. The molecular electrostatic potential (MESP) minimum at the fulvene π‐system (Vmin) and the change in MESP at any of the fulvene carbon atoms (ΔVC) for both neutral and reduced forms are used as excellent measures of substituent effect from the para and meta positions of the 1,3 and 6‐phenyl moieties. Substitution at 6‐phenyl para position has led to significant change in E0 than any other positions. By applying the additivity rule of substituent effects, an equation in ΔVC is derived to predict E0 for multiply substituted fulvenes. Further, E0 is predicted for a set of 2000 hexa‐substituted fulvene derivatives where the substituents and their positions in the system are chosen in a random way. The calculated E0 agreed very well with the experimental E0 reported by Godman et al. Predicting E0 solely by substituent effect offers a simple and powerful way to select suitable combinations of substituents on fulvene system for light harvesting applications. © 2018 Wiley Periodicals, Inc.

中文翻译：

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使用取代基效应的分子静电电位分析预测 1,3,6-三苯基富烯的还原电位

使用 B3LYP-SMD/6-311+G(d,p) 能级密度泛函理论研究了单和多取代基效应对 1,3,6-三苯基富烯的还原电位 (E0) 的影响。富烯 π 系统 (Vmin) 的分子静电势 (MESP) 最小值和中性和还原形式的任何富烯碳原子 (ΔVC) 处的 MESP 变化被用作对位和还原型取代基效应的极好量度。 1,3 和 6-苯基部分的间位。6-苯基对位取代导致 E0 比任何其他位置发生显着变化。通过应用取代基效应的可加性规则，推导出了 ΔVC 中的方程来预测多取代富烯的 E0。更多，E0 预测一组 2000 六取代富烯衍生物，其中取代基及其在系统中的位置以随机方式选择。计算的 E0 与 Godman 等人报告的实验 E0 非常吻合。仅通过取代基效应预测 E0 提供了一种简单而有效的方法，可以为富烯系统选择合适的取代基组合以用于光收集应用。© 2018 Wiley Periodicals, Inc.