Photophysical investigation into room-temperature emission from xanthene derivatives.

The photophysical consequences of replacing the nitrogen heteroatom in phenothiazine with methylene are investigated for both solutions and crystalline solids. We analysed the excited state dynamics of four xanthene derivatives and observed an anomalous fluorescence from an energy level higher than the S1 state with lifetimes between 2.8 ns and 5.8 ns in solution and as solids. Additionally, the solid-state xanthene derivatives exhibited long-lived emission consistent with a triplet excited state, displaying millisecond lifetimes that ranged from 0.1 ms to 3.4 ms at ambient temperature in air. Our findings were supported by optical studies, crystallographic structural analyses, and DFT computations, which corroborated the photophysical measurements. It was concluded that the presence of the nitrogen atom in phenothiazine is crucial for achieving ultra-long emission lifetimes and that these results contribute to a deeper understanding of excited state dynamics which have potential implications for applications, such as display technologies, anticounterfeiting technologies, and sensors.

Multiple aggregates from multiple polymorphs: structural and mechanistic insight into organic dye aggregates.

This case study provides evidence for the appearance of multiple aggregation forms of a single organic dye, arising from its packing polymorphs in the solid state. Each aggregate can be spectroscopically matched to one polymorph, acquiring nanoscopic structural information even in the absence of conventional H- or J-type aggregation spectral features. The conversion from one polymorphic aggregate to another supports the action of Ostwald's rule of stages in organic aggregates suspended in solution. Mechanistically, dye molecules from one aggregate dissociate then renucleate the more stable aggregate form, the first demonstration for an aggregation-induced emission-active organic dye.

Synthesis of Oligo(1,8-pyrenylene)s: A Series of Functional Molecular Liquids.

A monomer-through-pentamer series of oligo(1,8-pyrenylene)s was synthesized using a two-step iterative synthetic strategy. The trimer, tetramer, and pentamer are mixtures of atropisomers that interconvert slowly at room temperature (as shown by variable-temperature NMR analysis). They are liquids well below room temperature, as indicated by POM, DSC and SWAXS analysis. These oligomers are highly fluorescent both in the liquid state and in dilute solution (λF,max = 444-457 nm, φF = 0.80) and an investigation of their photophysical properties demonstrated that delocalization plays a larger role in their excited states than it does in related pyrene-based oligomers.

Modern Spin on the Electrochemical Persistence of Heteroatom-Bridged Triphenylmethyl-Type Radicals.

Herein we present a clarification of the ambiguous persistence of the 10-methyl-9-phenylacridanyl, 9-phenylxanthenyl, and 9-phenylthioxanthenyl radicals in electrochemical experiments. Each of these radicals has separately been the subject of conflicting literature results for decades with publications claiming both their chemical inertness and propensity to dimerize. We assert that each radical is persistent at conventional electrochemical time scales up to several minutes based on reversible redox couples and cyclic voltammogram simulations of the radicals and their respective cations. All three radicals are rapidly consumed by aerial O2, which lends irreversibility to the redox couples after fewer than 20 s of exposure to air. With appreciation for the O2 sensitivity of these radicals, their electrochemically generated UV-visible absorption spectra have been acquired and matched to predictions made by TD-DFT calculations. Further, we propose that previous claims to have electrochemically measured radical-radical dimerizations have only observed reaction of these radicals with dissolved O2.