Electrochemical carbon dioxide reduction (CO2R) has attracted a wide amount of attention as a potential means to reduce reliance on fossil fuels by converting CO2 into fuels and societally important chemicals. In particular, this technology has the potential to contribute to a closed carbon cycle when powered by low-carbon renewable energy sources. Amongst key challenges in advancing CO2R systems towards practical use is the development of non-precious metal catalysts that can selectively reduce CO2 into a single desired fuel and integrating them into a functional device. Molecular catalysts have long been studied as model systems for extracting important structure-activity relationships in CO2R because binding site, functional ligands and reaction environment can all be precisely defined. This offers particular advantages over heterogeneous catalysts which often have a diversity of possible active sites in generating fundamental insights that can later be translated to functional systems. To this end, most efforts in molecular CO2R have been directed in either using the catalysts in homogeneous form, dissolved in an electrolyte, or heterogenized onto an electrode surface. In aqueous electrolytes which are practical for CO2R, excessive hydrophobicity often precluded certain catalysts from being applied for CO2R as this prevented their dissolution for homogeneous applications or their capacity to effectively bind dissolved CO2 and extract protons from water when they were heterogenized.