Homoleptic tungsten(0) arylisocyanides possess photophysical and photochemical properties that rival those of archetypal ruthenium(II) and iridium(III) polypyridine complexes. Previous studies established that extending the π-system of 2,6-diisopropylphenylisocyanide (CNDipp) by coupling aryl substituents para to the isocyanide functionality results in W(CNDippAr)₆ oligoarylisocyanide complexes with greatly enhanced metal-to-ligand charge transfer (MLCT) excited-state properties relative to those of W(CNDipp)₆. Extending electronic modifications to delineate additional design principles for this class of photosensitizers, herein we report a series of W(CNAr)₆ compounds with naphthalene-based fused-ring (CN-1-(2-ⁱPr)-Naph) and CNDipp-based alkynyl-bridged (CNDipp^(CC)Ar) arylisocyanide ligands. Systematic variation of the secondary aromatic system in the CNDippCCAr platform provides a straightforward method to modulate the photophysical properties of W(CNDipp^(CC)Ar)₆ complexes, allowing access to an extended range of absorption/luminescence profiles and highly reducing excited states, while maintaining the high molar absorptivity MLCT absorption bands, high photoluminescence quantum yields, and long excited-state lifetimes of previous W(CNAr)₆ complexes. Notably, W(CN-1-(2-iPr)-Naph)₆ exhibits the longest excited-state lifetime of all W(CNAr)₆ complexes explored thus far, highlighting the potential benefits of utilizing fused-ring arylisocyanide ligands in the construction of tungsten(0) photoreductants
