Electronic structure design for nanoporous, electrically conductive zeolitic imidazolate frameworks

Electronic structure calculations are used to develop design rules for enhanced electrical conductivity in zeolitic imidazolate frameworks. The electrical resistivity of Co²⁺ based zeolitic imidazolate frameworks has previously been found to be ∼1000 times lower than that of Zn²⁺ based materials. The electrical conductivity of the frameworks can also be tuned by ligand molecule selection. Using density functional theory calculations, this controllable electrical conductivity is explained in terms of tuneable conduction band edge character, with calculations revealing the improved hybridisation and extended band character of the Co²⁺ frameworks. The improvements in the methylimidazolate frameworks are understood in terms of improved frontier orbital matching between metal and ligand. The modular tuneability and previously demonstrated facile synthesis provides a route to rational design of stable framework materials for electronic applications. By outlining these design principles we provide a route to the future development of stable, electrically conductive zeolitic imidazolate frameworks.