Unveiling the double triplet nature of the 2Ag state in conjugated stilbenoid compounds to achieve efficient singlet fission.

In this investigation, the excited-state evolution in a series of all-trans stilbenoid compounds, displaying a low-lying dark singlet state of 2Ag-like symmetry nearly degenerate with the bright 1Bu state, was unveiled by employing advanced ultrafast spectroscopies while probing the effect of solvent polarizability. Together with the dual emission, femtosecond transient absorption and broadband fluorescence up-conversion disclosed the double nature of the 2Ag-like state showing both singlet features, a lifetime typical of a singlet and the ability to emit, and a triplet character, exhibiting a triplet-like absorption spectrum. The ultrafast formation (in hundreds of femtoseconds) from the non-relaxed upper singlet state led to the identification of 2Ag as the correlated triplet pair of singlet fission. The spectral difference obtained by comparison of transient absorption peaks of the 2Ag (1TT) and the triplet states was found to be in remarkable agreement with the observed triplet yield and the 1(TT) separation rate constant. Indeed, this spectral shift provided an experimental method to gain qualitative insight into the ease of separation of the 1(TT) and the relative SF efficiency. The highly conjugated polyene-like structures enable the ultrafast formation of the double triplet, but then the large binding energy prevents the triplet separation and thus the effective completion of singlet fission. Even though thermodynamically feasible for all the investigated stilbenoids according to TD-DFT calculations, singlet fission resulted to occur efficiently in the case of 1-(pyridyl-4-ylethenyl)-4-(p-nitrostyryl)benzene and nitro-styrylfuran with the triplet yield reaching 120% and 140%, respectively, triggered by their greatly enhanced intramolecular charge transfer character relative to the other compounds in the series.

Lighting-Up the Far-Red Fluorescence of RNA-Selective Dyes by Switching from Ortho to Para Position.

Fluorescence imaging is constantly searching for new far-red emitting probes whose turn-on response is selective upon the interaction with specific biological targets. Cationic push-pull dyes could indeed respond to these requirements due to their intramolecular charge transfer (ICT) character, by which their optical properties can be tuned, and their ability to interact strongly with nucleic acids. Starting from the intriguing results recently achieved with some push-pull dimethylamino-phenyl dyes, two isomers obtained by switching the cationic electron acceptor head (either a methylpyridinium or a methylquinolinium) from the ortho to the para position have been scrutinized for their ICT dynamics, their affinity towards DNA and RNA, and in vitro behavior. By exploiting the marked fluorescence enhancement observed upon complexation with polynucleotides, fluorimetric titrations were employed to evaluate the dyes' ability as efficient DNA/RNA binders. The studied compounds exhibited in vitro RNA-selectivity by localizing in the RNA-rich nucleoli and within the mitochondria, as demonstrated by fluorescence microscopy. The para-quinolinium derivative showed some modest antiproliferative effect on two tumor cell lines as well as improved properties as an RNA-selective far-red probe in terms of both turn-on response (100-fold fluorescence enhancement) and localized staining ability, attracting interest as a potential theranostic agent.

Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution.

The identification of novel molecular systems with high fluorescence and significant non-linear optical (NLO) properties is a hot topic in the continuous search for new emissive probes. Here, the photobehavior of three two-arm bis[(dimethylamino)styryl]benzene derivatives, where the central benzene was replaced by pyridine, furan, or thiophene, was studied by stationary and time-resolved spectroscopic techniques with ns and fs resolution. The three molecules under investigation all showed positive fluorosolvatochromism, due to intramolecular charge-transfer (ICT) dynamics from the electron-donor dimethylamino groups, and significant fluorescence quantum yields, because of the population of a planar and emissive ICT state stabilized by intramolecular hydrogen-bond-like interactions. The NLO properties (hyperpolarizability coefficient and TPA cross-section) were also measured. The obtained results allowed the role of the central heteroaromatic ring to be disclosed. In particular, the introduction of the thiophene ring guarantees high fluorescent quantum yields irrespective of the polarity of the medium, and the largest hyperpolarizability coefficient because of the increased conjugation. An important and structure-dependent involvement of the triplet state was also highlighted, with the intersystem crossing being competitive with fluorescence, especially in the thiophene derivative, where the triplet was found to significantly sensitize molecular oxygen even in polar environment, leading to possible applications in photodynamic therapy.