Abstract

Developing predictive tools for the elucidation of redox and optical properties of polychromophoric assemblies is crucial for the rational design of efficient charge-transfer materials. Here, such tools are introduced to explain the curious observation that a pair of bichromophoric electron donors based on ethanoanthracene (5) and dihydroanthracene (DHA or 11), having similar interchromophoric separation between the carbons in the region of orbital overlap, show dramatically different (>300 mV) stabilization of their cation radicals. Analysis of molecular orbital diagrams reveals the important interplay between through-space and through-bond electronic couplings, which results in HOMO/HOMO–1 swapping in 11 (HOMO = highest occupied molecular orbital). Unlike the antisymmetric singly occupied molecular orbital (SOMO) that stabilizes a hole by charge resonance in 5•+ (0.57 V), the symmetric SOMO in 11•+ (0.88 V) does not afford hole stabilization by charge resonance; rather, the hole localizes onto a single ...

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