Excited-State Triplet Equilibria in a Series of Re(I)-Naphthalimide Bichromophores

We present the synthesis, structural characterization, electronic structure calculations, and the ultrafast and supra-nanosecond photophysical properties of a series of five bichromophores of the general structural formula [Re(5-R-phen)(CO) 3 (dmap)](PF 6 ), where R is a naphthalimide (NI), phen = 1,10-phenanthroline, and dmap is 4-dimethylaminopyridine. The NI chromophores were systematically modified at their 4-positions with -H ( NI ), -Br ( BrNI ), phenoxy ( PONI ), thiobenzene ( PSNI ), and piperidine ( PNI ), rendering a series of metal-organic bichromophores ( Re1 - Re5 , respectively) featuring variability in the singlet and triplet energies in the pendant NI subunit. Five closely related organic chromophores as well as [Re(phen)(CO) 3 (dmap)](PF 6 ) ( Re6 ) were investigated in parallel to appropriately model the photophysical properties exhibited in the bichromophores. The excited state processes of all molecules in this study were elucidated using a combination of transient absorption spectroscopy and time-resolved photoluminescence (PL) spectroscopy, revealing the kinetics of the energy transfer processes occurring between the appended chromophores. The spectroscopic analysis was further supported by electronic structure calculations which identified the origin of many of the experimentally observed electronic transitions.