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Although perhaps thousands of ILs have been reported in the literature , many are essentially built upon the same structure: 1 ,3-difunctionalized imidazolium cations. While these difunctionalized cations offer immense possibilities for tuning structure-property relationships , it is well-known that imidazolium-based materials can be further tailored via the introduction of various functionalities at the positions within the imidazole ring. However , strategies which employ trifunctionalized (or greater) imidazolium cations are seldom employed in materials design. Our group has synthesized a library of imidazole-based precursors via a scalable synthetic technique so as to further explore imidazolium cations with greater degrees of functionality , with focus on new solvents , polymers , composites , and liquid crystalline materials. This presentation will address the challenges and opportunities of branching out the imidazole ring so as to gain new dimensions for materials design and the potential implications in applications such as polymer membrane separations for energy applications (e.g. CO2capture) and self-assembly.