The UV-Vis absorption spectrum of the Pt(II) complex 1 (see ESI S36) features an intense band in the UV region, primarily attributed to intraligand ( 1 IL) and metal-perturbed interligand charge 20 transfer ( 1 ILCT) states. Additionally, a broad band between 350-450 nm is ascribed to a mixture of spin-allowed metal-to-ligand charge transfer ( 1 MLCT) and intraligand ( 1 IL) transitions, as commonly observed in this class of compounds . In contrast, the absorption spectrum of complex 2 (see ESI S37) in dilute solution (10 -4 M, ACN) shows intense absorptions in the 250-350 nm range, attributed to 1 IL and 1 ILCT transitions, while 1 MLCT absorptions are presumed to be at very high energies and are thus obscured by the ligand-centered transitions, consistent with observations in other Pt(IV) complexes . Interestingly, irradiating a dilute solution of complex 2 (10 -4 M in ACN) with a deuterium lamp results in the reductive photodissociation of the chloride ligands, forming complex 1. This transformation is followed by UV-Vis absorption spectra (see ESI S38), and the identity of the species is verified by NMR spectroscopy (see ESI 5 S7). When this photoconversion is performed in the same medium and concentration where gels G1 and G2 were chemically formed, no gelation occurs; instead, the growth of luminescent fibers was observed (see ESI S39-S43 for photophysical characterization). SEM analysis of the aggregates formed by photoreduction reveals a network of lightly curved wires, similar to those obtained with G1 and G2 (see ESI S44-S45).