Modeling energy transfer and absorption spectra in layered metal–organic frameworks based on a Frenkel–Holstein Hamiltonian

Optimizing energy and charge transfer is key in design and implementation of efficient layered conductive metal–organic frameworks (MOFs) for practical applications. In this work, for the first time, we investigate the role of both long-range excitonic and short-range charge transfer coupling as well as their dependency on reorganization energy on through-space charge transfer in layered MOFs. A π-stacked model system is built based on the archetypal Ni3(HITP)2, HITP = 2,3,6,7,10,11-hexaiminotriphenylene, layered MOF, and a Frenkel/charge transfer Holstein Hamiltonian is developed that takes into account both electronic coupling and intramolecular vibrations. The dependency of the long- and short-range couplings of secondary building units (SBUs) on the stacking geometry is evaluated, which predicts that photophysical properties of layered MOFs critically depend on the degree of ordering between layers. We show that the impact of the two coupling sources in these materials can be discerned or enhanced by the displacement of the SBUs along the long or short molecular axes. The effects of vibronic spectral signatures are examined in both perturbative and resonance regimes. Although, to the best of our knowledge, displacement engineering in layered MOFs currently remains beyond reach, the findings reported here offer new details on the photophysical structure–property relationships in layered MOFs and provide suggestions on how to combine elements of molecular design and engineering to achieve desirable properties and functions for nano- and mesoscale optoelectronic applications