Molecular fluorophore dimerization: a new paradigm for precision phototheranostics

Abstract

Molecular fluorophore dimerization has recently emerged as a powerful and versatile design strategy in phototheranostics, offering a distinct regulatory regime that is fundamentally different from conventional single-molecule, polymeric, or aggregate-based systems. In this review, we present the first systematic and unified analysis of molecular dimerization as an independent paradigm for precision phototheranostics. Unlike previous reviews that primarily focus on isolated small-molecule fluorophores, polymeric architectures, or aggregates, this work highlights dimeric systems as an intermediate yet well-defined state that bridges molecular-level precision and collective-level functionality. We first comprehensively elucidate the fundamental photophysical mechanisms governing dimerization, and demonstrate how these processes uniquely regulate excited-state dynamics. Then, we reveal how dimerization enhances biophysical performance, such as controllable self-assembly and improved tumor accumulation. Representative dimeric systems across multiple dye families, including BODIPY, cyanine, porphyrins, donor–acceptor molecules, and metal complexes, are systematically categorized and analyzed, with an emphasis on structure–activity relationships and dimer-specific functional advantages in imaging-guided therapy. Finally, we discuss the current challenges and outline future directions, especially for artificial-intelligence-assisted molecular design. By positioning molecular dimerization as a distinct intermediate state between single molecules and higher-order assemblies, this review provides conceptual clarity and design principles for the development of next-generation phototheranostic agents.