Drawing inspiration from nature's enzymatic processes, we design transition metal frameworks that integrate catalytic activity with light harvesting to transform earth-abundant resources into valuable chemicals. By employing redox-active organic cofactors such as flavins and quinones as multifunctional ligands, we enhance metal-ligand cooperativity, facilitating efficient proton and electron transfer in both ground and excited states. Centering on the heterocyclic (iso)alloxazine core of flavin, we have developed a bidentate ligand that fosters hydrogen bonding within the secondary coordination sphere. When coordinated with various late first-row transition metals, these ligands form octahedral complexes that interact with (pseudo)halides through hydrogen bonding. Upon the introduction of a base, tautomerization of the ligand occurs, resulting in metal complexes bound to water, alcohol, or ammonia. This study highlights flavin as a versatile ligand scaffold, providing a tunable strategy for designing transition metal catalysts with improved reactivity and selectivity.