Rational modifications of PCN-700 to induce electrical conductivity: a computational study

Area of Science:

• Materials Science
• Nanotechnology
• Computational Chemistry

Background:

• Metal-organic frameworks (MOFs) are nanoporous materials with emerging applications.
• Electrical conductivity in MOFs is a recent discovery, with few conductive examples available.
• Developing strategies to induce electrical conductivity in MOFs is crucial for their broader use.

Purpose of the Study:

• To computationally investigate the rational modification of an insulating MOF (PCN-700) to achieve electrical conductivity.
• To explore the design principles for creating conductive MOFs through framework engineering.
• To identify pathways for through-bond charge transport (CT) in MOFs.

Main Methods:

• Computational study involving rational modifications of the PCN-700 MOF structure.
• Introduction of electroactive DHBQ linkers via sequential linker installation.
• Metal substitution (Zr4+ with Ce4+) and linker saturation to optimize energy level alignment for charge transport.

Main Results:

• Predicted electrical conductivity in the modified MOF, Ce-PCN-700-DHBQ.
• Identified semiconducting behavior with a predicted bandgap of 2.09 eV.
• Demonstrated that chemical environment modifications can further reduce the bandgap.

Conclusions:

• Rational framework modifications can successfully induce electrical conductivity in previously insulating MOFs.
• The study highlights the critical role of energy level matching in designing conductive MOFs.
• The findings provide a design strategy for developing new electrically conductive MOFs.