The non-siderophoric Fe3+ photocage FerriCast (4,5-dimethoxy-2-nitrophenyl)-[4-(1-oxa-4,10-dithia-7-aza-cyclodo-dec-7-yl)phenyl] methanol (2) has been prepared in high yield using an optimized two-step reaction sequence that utilizes a trimethylsilyl trifluoromethanesulfonate (TMSOTf) assisted electrophilic aromatic substitution as the key synthetic step. Spectrophotometric assessment of Fe3+ binding to FerriCast revealed a binding stoichiometry and metal ion affinity dependent on the nature of the counterion. Exposure of FerriCast to 350 nm light initiates a photoreaction that converts FerriCast into FerriUnc (4,5-dimethoxy-2-nitrosophenyl)-[4-(1-oxa-4,10-dithia-7-aza-cyclcdodec-7 -yl)phenyl]-methanone), which binds Fe3+ less strongly owing to resonance delocalization of the anilino lone pair into the benzophenone A-system, The release of Fe3+ upon photolysis of FerriCast also was evaluated using a previously reported turn-on fluorescent sensor that utilizes the same macrocyclic ligand (4-(1-oxa-4,10-dithia-7-aza-cyclcdodec-7-yl)phenyl, AT(2)12C4). In contrast to the original reports on AT(2)12C4-based Fe3+ sensors, FerriCast does not interact with ferric iron in aqueous solution. Introduction of oxygen containing solvents (MeOH, H2O, DMSO, MES, and phosphate buffers) to CH3CN solutions of metalated FerriCast lead to rapid decomplexation as measured by UV-visible spectroscopy. Further investigations contradicted the published conclusions on the aqueous coordination chemistry of AT(2)12C4, but also confirmed the unique and unexpected selectivity of the macrocycle for Fe3+ in nonaqueous solvents. The crystallographic analysis of [Cu(AT(2)12C4)Cl](+) provides a rare example of a bifurcated hydrogen bond, and evidence for redox chemistry with the ligand. Spectrophotometric analysis of the model ligand with redox active metal ions provide evidence for AT(2)12C4(-+) a quasi-stable species the presence of which suggests caution should be taken when evaluating the interaction of aniline-containing systems with redox active metal ions.