Excited-state relaxation in two prototypical shortwave infrared (SWIR) polymethine dyes developed for bioimaging, heptamethine chromenylium Chrom7 and flavylium Flav7, is studied by means of femtosecond transient absorption with broadband ultraviolet-to-SWIR probing complemented by steady-state and time-resolved fluorescence and phosphorescence measurements. The relaxation processes of the dyes in dichloromethane are resolved with sub-100 fs temporal resolution using SWIR, near-IR, and visible photoexcitation. Different population members of the ground-state inhomogeneous ensemble are found to equilibrate skeletal deformation changes with time constants of 90 fs and either 230 fs (Chrom7) and 350 fs (Flav7) followed by slower evolution matching the 1-ps timescale of diffusive solvation dynamics.
View Article and Find Full Text PDFExcited-state dynamics of -4,4'-azopyridine in ethanol is studied using femtosecond transient absorption with 30 fs temporal resolution. Exciting the system at three different wavelengths, 460 and 290 (275) nm, to access the S * and S * electronic states, respectively, reveals a 195 cm vibrational coherence, which suggests that the same mode is active in both * and * relaxation channels. Following S-excitation, relaxation proceeds via a nonrotational pathway, where a fraction of the * population is trapped in a planar minimum (lifetime, 2.
View Article and Find Full Text PDFColloidal semiconductor nanocrystals (NCs) represent a promising class of nanomaterials for lasing applications. Currently, one of the key challenges facing the development of high-performance NC optical gain media lies in enhancing the lifetime of biexciton populations. This usually requires the employment of charge-delocalizing particle architectures, such as core/shell NCs, nanorods, and nanoplatelets.
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