The synthesis and characterization of porous, conductive, and ordered materials

Abstract

Two different classes of polymers were pursued as candidates for materials possessing porosity, conductivity, and crystalline order. Attempts were made with hexaazatrinaphthylene- and dibenzotetrathiafulvalene-based precursors with boronic acids to prepare covalent-organic frameworks (COFs) possessing boroxole linkages. After preparing the precursors, several different reaction conditions were attempted, but the desired COFs proved elusive. The second class of materials was tetrathiafulvalene-based metal-organic frameworks (MOFs). These materials were constructed with tetrathiafulvalene tetrabenzoic acid and zinc, cobalt, and manganese nitrate to give helical structures with approximately cylindrical pores. This structure type has one close S-S contact of 3.8 Å which acts as a potential avenue for charge transfer. Gas sorption measurements suggest that the materials retain porosity upon evacuation. The material possesses high charge mobility as determined by flash photolysis time-resolved microwave conductivity measurements.