Flavylium compounds are versatile molecules that comprise anthocyanins, the ubiquitous colorants used by Nature to confer colour to most flowers and fruits. They have found a wide range of applications in human technology, from the millenary colour paints described by the Roman architect Vitruvius, to their use as food additives, combining colour and antioxidant effects, and even as light absorbers in solar cells aiming at a greener solar energy conversion. Their rich complexity derives in part from their ability to switch between a variety of species (flavylium cations, neutral quinoidal bases, hemiketals and chalcones, and negatively charged phenolates) by means of external stimuli, such as pH, temperature and light. This critical review describes (i) the historical advancements in the understanding of the equilibria of their chemical reaction networks; (ii) their thermodynamics and kinetics; (iii) the mechanisms underlying their colour development, such as co-pigmentation and host–guest interactions; (iv) the photophysics and photochemistry that lead to photochromism; and (v) applications in solar cells, models for optical memories, photochromic soft materials such as ionic liquids and gels, and their properties in solid state materials (274 references).

Gold(I) alkynyl complexes present a growing research field with respect to their very wide range of applications in different areas such as luminescence, molecular recognition, optical switches, electronics and catalysis. Biological applications are also being developed in the recent years, where these complexes are used as therapeutic agents against different illnesses such as cancer cells or malaria. Related to luminescence, a general overview of the different states responsible for the observed emission is also included in this critical review. In some cases, the assignment is complicated due to the influence of the gold(I) atom and its capability to form metal⋯metal interactions (aurophilicity). Although an extensive discussion has been found in the literature related to the luminescent properties of these complexes, to the best of our knowledge there are not reports covering the span of their very interesting applications. The widespread research fields where this kind of complexes could present a key role is presented in this review (119 references).

Photothermal Therapy (PTT) impact in cancer therapy has been increasing due to the enhanced photothermal capabilities of a new generation of nanoscale photothermal agents. Among these nanoscale agents, gold nanoshells and nanorods have demonstrated optimal properties for translation of near infra-red radiation into heat at the site of interest. However, smaller spherical gold nanoparticles (AuNPs) are easier to produce, less toxic and show improved photoconversion capability that may profit from the irradiation in the visible via standard surgical green lasers. Here we show the efficient light-to-heat conversion of spherical 14 nm AuNPs irradiated in the visible region (at the surface plasmons resonance peak) and its application to selectively obliterate cancer cells. Using breast cancer as model, we show a synergistic interaction between heat (photoconversion at 530 nm) and cytotoxic action by doxorubicin with clear advantages to those of the individual therapy approaches.

Dual luminescence, i.e. intense, simultaneous, room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) is observed in a series of donor–acceptor–donor (D–A–D) molecules. This dual luminescence is stronger in the “angular” isomers, compared to their “linear” regioisomers, which is consistent with an enhanced intersystem crossing (ISC) in the former. Herein, we demonstrate that the small energy gap between the triplet levels, T₁–T_n, below the lowest singlet state, S₁, in the “angular” regioisomers, enhances the coupling between S₁ and T₁ states and favors ISC and reverse ISC (rISC). This is consistent with a spin–vibronic mechanism. In the absence of this “triplet ladder”, due to the larger energy difference between T₁ and T_n in the “linear” regioisomers, the ISC and rISC are not efficient. Remarkably, the enhancement of the ISC rate in the “angular” regioisomers is accompanied by an increase of the rate of internal conversion (IC). These results highlight the contributions of higher triplet excited states and molecular vibronic coupling to the harvest of triplet states in organic compounds, and cast the TADF and RTP mechanisms into a common conceptual framework.

Seven flavylium salt dyes were employed for the first time as sensitizers for dye-sensitized solar cells (DSSCs). The theoretical and experimental wavelengths of the maximum absorbances, the HOMO and LUMO energy levels, the coefficients, the oscillator strengths and the dipole moments are calculated for these synthetic dyes. The introduction of a donor group in the flavylium molecular structure was investigated. Photophysical and photoelectrochemical measurements showed that some of these synthetic analogues of anthocyanins are very promising for DSSC applications. The best performance was obtained by a DSSC based on the novel compound 7-(N,N-diethylamino)-3′,4′-dihydroxyflavylium which produced a 2.15% solar energy-to-electricity conversion efficiency, under AM 1.5 irradiation (100 mW cm⁻²) with a short-circuit current density (J_sc) of 12.0 mA cm⁻², a fill factor of 0.5 and an open-circuit voltage (V_oc) of 0.355 V; its incident photocurrent efficiency of 51% at the peak of the visible absorption band of the dye is remarkable. Our results demonstrated that the substitution of a hydroxylic group with a diethylamine unit in position 7 of ring A of the flavylium backbone expanded the π-conjugation in the dye and thus resulted in a higher absorption in the visible region and is advantageous for effective electron injection from the dye into the conduction band of TiO₂.