title: Bespoke photoreductants: tungsten arylisocyanides.
abstract: Modular syntheses of oligoarylisocyanide ligands that are derivatives of 2,6-diisopropylphenyl isocyanide (CNdipp) have been developed; tungsten complexes incorporating these oligoarylisocyanide ligands exhibit intense metal-to-ligand charge-transfer visible absorptions that are red-shifted and more intense than those of the parent W(CNdipp)6 complex. Additionally, these W(CNAr)6 complexes have enhanced excited-state properties, including longer lifetimes and very high quantum yields. The decay kinetics of electronically excited W(CNAr)6 complexes (*W(CNAr)6) show solvent dependences; faster decay is observed in higher dielectric solvents. *W(CNAr)6 lifetimes are temperature dependent, suggestive of a strong coupling nonradiative decay mechanism that promotes repopulation of the ground state. Notably, *W(CNAr)6 complexes are exceptionally strong reductants: [W(CNAr)6](+)/*W(CNAr)6 potentials are more negative than -2.7 V vs [Cp2Fe](+)/Cp2Fe.
authors.affiliation: Beckman Institute, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Wesley
authors.initials: W
authors.lastname: Sattler
authors.forename: Lawrence M
authors.initials: LM
authors.lastname: Henling
authors.forename: Jay R
authors.initials: JR
authors.lastname: Winkler
authors.forename: Harry B
authors.initials: HB
authors.lastname: Gray