Regulating electron transfer and orbital interaction within metalloporphyrin-MOFs for highly sensitive NO sensing.

The understanding of electron transfer pathways and orbital interactions between analytes and adsorption sites in gas-sensitive studies, especially at the atomic level, is currently limited. Herein, we have designed eight isoreticular catechol-metalloporphyrin scaffolds, FeTCP-M and InTCP-M (TCP = 5,10,15,20-tetrakis-catechol-porphyrin, M = Fe, Co, Ni and Zn) with adjustable charge transfer schemes in the coordination microenvironment and precise tuning of orbital interactions between analytes and adsorption sites, which can be used as models for exploring the influence of these factors on gas sensing. Our experimental findings indicate that the sensitivity and selectivity can be modulated using the type of metals in the metal-catechol chains (which regulate the electron transfer routes) and the metalloporphyrin rings (which fine-tune the orbital interactions between analytes and adsorption sites).

Topologically Tunable Conjugated Metal-Organic Frameworks for Modulating Conductivity and Chemiresistive Properties for NH Sensing.

Electrically conductive metal-organic frameworks (cMOFs) have garnered significant attention in materials science due to their potential applications in modern electrical devices. However, achieving effective modulation of their conductivity has proven to be a major challenge. In this study, we have successfully prepared cMOFs with high conductivity by incorporating electron-donating fused thiophen rings in the frameworks and extending their π-conjugated systems through ring-closing reactions.