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Medium viscosity strongly affects the dynamics of solvated species and can drastically alter the deactivation pathways of their excited states. This study demonstrates the utility of poly(dimethylsiloxane) (PDMS) as a room-temperature solid-state medium for optical spectroscopy. As a thermoset elastic polymer, PDMS is transparent in the near ultraviolet, visible, and near infrared spectral regions. It is easy to mould into any shape, forming surfaces with a pronounced smoothness. While PDMS is broadly used for the fabrication of microfluidic devices, it swells in organic solvents, presenting severe limitations for the utility of such devices for applications employing non-aqueous fluids. Nevertheless, this swelling is reversible, which proves immensely beneficial for loading samples into the PDMS solid matrix. Transferring molecular-rotor dyes (used for staining prokaryotic cells and amyloid proteins) from non-viscous solvents into PDMS induces orders-of-magnitude enhancement of their fluorescence quantum yield and excited-state lifetimes, providing mechanistic insights about their deactivation pathways. These findings demonstrate the unexplored potential of PDMS as a solid solvent for optical applications. 

Medium polarity plays a crucial role in charge-transfer processes and electrochemistry. The added supporting electrolyte in electrochemical setups, essential for attaining the needed electrical conductivity, sets challenges for estimating medium polarity. Herein, we resort to Lippert–Mataga–Ooshika (LMO) formalism for estimating the Onsager polarity of electrolyte organic solutions pertinent to electrochemical analysis. An amine derivative of 1,8-naphthalimide proves to be an appropriate photoprobe for LMO analysis. An increase in electrolyte concentration enhances the polarity of the solutions. This effect becomes especially pronounced for low-polarity solvents. Adding 100 mM tetrabutylammonium hexafluorophosphate to chloroform results in solution polarity exceeding that of neat dichloromethane and 1,2-dichloroethane. Conversely, the observed polarity enhancement that emerges upon the same electrolyte addition to solvents such as acetonitrile and N,N-dimethylformamide is hardly as dramatic. Measured refractive indices provide a means for converting Onsager to Born polarity, which is essential for analyzing medium effects on electrochemical trends. This study demonstrates a robust optical means, encompassing steady-state spectroscopy and refractometry, for characterizing solution properties important for charge-transfer science and electrochemistry. 

Intermediate donor–acceptor electronic coupling leads to a brilliant fluorescence behaviour. Charge transfer (CT) is key for molecular photonics, governing the optical properties of chromophores comprising electron-rich and electron-deficient components. In photoexcited dyes with an acceptor– donor–acceptor or donor–acceptor–donor architecture, CT breaks their quadrupolar symmetry and yields dipolar structures manifesting pronounced solvatochromism. Herein, we explore the effects of electronic coupling through biaryl linkers on the excited-state symmetry breaking of such hybrid dyes composed of an electron-rich core, i.e., 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP), and pyrene substituents that can act as electron acceptors. Experimental and theoretical studies reveal that strengthening the donor–acceptor electronic coupling decreases the CT rates and the propensity for symmetry breaking. We ascribe this unexpected result to effects of electronic coupling on the CT thermodynamics, which in its turn affects the CT kinetics. In cases of intermediate electronic coupling, the pyrene-DHPP conjugates produce fluorescence spectra, spreading over the whole visible range, that in addition to the broad CT emission, show bands from the radiative deactivation of the locally excited states of the donor and the acceptors. Because the radiative deactivation of the low-lying CT states is distinctly slow, fluorescence from upper locally excited states emerge leading to the observed anti- Kasha behaviour. As a result, these dyes exhibit white fluorescence. In addition to demonstrating the multifaceted nature of the effects of electronic coupling on CT dynamics, these chromophores can act as broad-band light sources with practical importance for imaging and photonics. 

Natural dyes and pigments offer incomparable diversity of structures and functionalities, making them an excellent source of inspiration for the design and development of synthetic chromophores with a myriad of emerging properties. Formed during maturation of red wines, pyranoanthocyanins are electron-deficient cationic pyranoflavylium dyes with broad absorption in the visible spectral region and pronounced chemical and photostability. Herein, we survey the optical and electrochemical properties of synthetic pyranoflavylium dyes functionalized with different electron-donating and electron-withdrawing groups, which vary their reduction potentials over a range of about 400 mV. Despite their highly electron-deficient cores, the exploration of pyranoflavyliums as photosensitizers has been limited to the “classical” n-type dye-sensitized solar cells (DSSCs) where they act as electron donors. In light of their electrochemical and spectroscopic properties, however, these biomimetic synthetic dyes should prove to be immensely beneficial as chromophores in p-type DSSCs, where their ability to act as photooxidants, along with their pronounced photostability, can benefit key advances in solar-energy science and engineering. 

The electronically excited singlet states of nitroaromatic compounds are often presumed to be essentially non-fluorescent. Nonetheless, a growing number of reports in the literature have demonstrated that certain structural types of nitroaromatics can indeed fluoresce, and often quite efficiently. Consideration of the mechanisms responsible for the typical fast or ultrafast non-radiative deactivation of the excited singlet states of nitroaromatics points to several general principles for their design that combine the strong electron-withdrawing properties of the nitro group with reasonable fluorescence quantum yields. An overview of published examples of fluorescent nitroaromatics emphasizes these concepts in the context of the importance of chromophore architecture and conformation and the defining roles of excited state charge transfer and solvent polarity in modulating the non-radiative decay channels that compete with fluorescence. Overcoming the stigma that nitroaromatics are intrinsically destined to be non-fluorescent thus paves the way for incorporating the strongly electron-withdrawing nitro group into the existing toolbox for the development of new nitro-substituted fluorophores and chromophores tuned to specific applications.