Chromophore networks are the active component in biological optoelectronic systems, such as photosynthetic complexes. These systems have shown that, by controlling the structural and energetic characteristics, high transport efficiencies are obtainable. Likewise, DNA-templated chromophore networks allow the precise structural control of chromophores, making them good candidates for biomimetic functional materials. Their well-established procedures for the customization and duplication of DNA are also especially suitable for modular design strategies to test large sample libraries. However, the improved structural and energetic control of large sample libraries creates a need for nanoscale characterization using routine measurements, such as linear absorption and circular dichroism. A network’s photoreactivity depends on its state energies, couplings, structural arrangement, and disorder characteristics. Here, experimental measurements are combined with genetic algorithms and modeling to find the molecular characteristics of these structures. This approach yields the system Hamiltonian, static and dynamic broadening contributions, and aggregate structures of molecular networks (Figure 1). Temperature-dependent measurements further characterize the sources of disorder. Collectively, these approaches obtain the information needed to understand chemical structures and perform subsequent energy-transport modeling.

Understanding energy levels and structures in modular chromophore networks templated by DNA

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