Design Principles for Singlet Fission in Aza-BODIPY Dimers: Spacer-Controlled Electronic Structure and Energy Ordering

Abstract

In this work, we investigate the role of spacers in tuning singlet-fission (SF) activity in aza-BODIPY dimers using a diabatic electronic-structure framework. A series of nine spacer-linked dimers is analyzed employing high-level multireference methods to evaluate the energetics and couplings of the locally excited (LE), charge-transfer (CT), and multiexcitonic (ME) states. The introduction of spacers reduces excessive state mixing that was observed in C-C bonded aza-BODIPY dimers and promotes the emergence of more distinct ME states, while preserving the CT-mediated interactions required for efficient SF. Furthermore, the substitution pattern, degree of conjugation, and introduction of acetylene units strongly modulate the relative state energetics and effective couplings, thereby tuning the SF rate over several orders of magnitude. These findings establish clear structure--property relationships and provide molecular design guidelines for optimizing SF activity in aza-BODIPY-based chromophores.