Efficient Syntheses of Porous Covalent Frameworks of High Surface Area and Tunable Electroactivity

This synthetic project aims for robust covalent solids combining porous structures and highly electroactive metal-thiolate functions (i.e., the metal-dithiolene hybrid motif), in order to fundamentally impact the wide-ranging technologies of sensors, heterogeneous catalysis, and photoelectrochemical cells and batteries. The metal-dithiolene unit is famous for its strength, well-defined geometry, and versatile electroactive properties. However, the integration of this motif into stable porous solids remains a challenge because of the apparent dilemma traditionally believed to be existent between bond strength and crystallinity: namely, the very strong metal-thiolate bonds often form too fast and irreversibly, and the resultant framework solids tend to be ill-ordered and nonporous. Combining the recent advances in the making of porous framework materials and our unique specialty in molecular design/synthesis, we plan to synthesize rigid, multidentate dithiolene building blocks that will bind metal ions in well-defined local geometry, thus enforcing substantial porosity throughout the resultant frameworks: i.e., even in an amorphous or semi-crystalline state, the highly rigid and open framework product will be constraint to yield the desired porous properties.