A set of 3-ethynylaryl coumarin dyes with mono, bithiophenes and the fused variant, thieno [3,2-b] thiophene, as well as an alkylated benzotriazole unit were prepared and tested for dye-sensitized solar cells (DSSCs). For comparison purposes, the variation of the substitution pattern at the coumarin unit was analyzed with the natural product 6,7-dihydroxycoumarin (Esculetin) as well as 5,7-dihydroxycomarin in the case of the bithiophene dye. Crucial steps for extension of the conjugated system involved Sonogashira reaction yielding highly fluorescent molecules. Spectroscopic characterization showed that the extension of conjugation via the alkynyl bridge resulted in a strong red-shift of absorption and emission spectra (in solution) of approximately 73–79 nm and 52–89 nm, respectively, relative to 6,7-dimethoxy-4-methylcoumarin (labs = 341 nm and lem = 410 nm). Theoretical density functional theory (DFT) calculations show that the Lowest Unoccupied Molecular Orbital (LUMO) is mostly centered in the cyanoacrylic anchor unit, corroborating the high intramolecular charge transfer (ICT) character of the electronic transition. Photovoltaic performance evaluation reveals that the thieno [3,2-b] thiophene unit present in dye 8 leads to the best sensitizer of the set, with a conversion efficiency (η = 2.00%), best VOC (367 mV) and second best Jsc (9.28 mA·cm−2), surpassed only by dye 9b (Jsc = 10.19 mA·cm−2). This high photocurrent value can be attributed to increased donor ability of the 5,7-dimethoxy unit when compared to the 6,7 equivalent (9b).

A pH-, light- and redox-responsive flavylium-bipyridinium molecular dyad (bioinspired in natural anthocyanins) was synthesized and employed to devise a pseudorotaxane with the macrocycle cucurbit[7]uril (CB7) in aqueous solution. The inclusion complex was characterized by UV-Vis absorption, fluorescence emission, NMR and electrochemical techniques which demonstrate formation of a stable binary complex between the dyad and CB7 both under acidic and neutral conditions. It is noteworthy that the flavylium-bipyridinium tricationic dyad is only stable in highly acidic media, undergoing a reversible hydration reaction at slightly acidic or neutral pH to give a trans-chalcone-bipyridinium dication. 1H NMR experiments showed that in this last species the CB7 binds to the bipyridinium unit while in the tricationic species the macrocycle is positioned between the flavylium and the bipyridinium moieties. The different location of the CB7 wheel in the two dyad states allows control of the shuttling movement using light and pH stimuli that trigger the interconversion between these two species.

The use of ionic liquid and organic salts as additives for electrolyte systems in dye-sensitized solar cells have been widely described in recent years. The tunability of their physical-chemical properties according to the cation–anion selection contributes toward their high efficiencies. For this purpose, several iodide-based organic salts including imidazolium, picolinium, guanidinium and alkylammonium cations were tested using acetonitrile/valeronitrile electrolytes and their photovoltaic parameters were compared. A best efficiency of 4.48% (4.15% for the reference) was found for 1-ethyl-2,3-dimethylimidazolium iodide ([C2DMIM]I) containing electrolyte, reaffirming the effectiveness of these additives. 4-tertbutylpyridine was included into the formulation to further improve the performance while determining which iodide salts demonstrate the highest synergy with this additive. [C2DMIM]I once again proved to be the superior additive, achieving an efficiency of 6.48% (6% for the reference). Electrochemical impedance spectroscopy was employed to elucidate the effects of the various additives, demonstrating the relevance of the counter electrode resistance on device performance. Finally, several computational descriptors for the cationic structures were calculated and correlated with the photovoltaic and resistance parameters, showing that properties related to polarity, namely relative positive charge, molecular polarizability and partition coefficient are in good agreement with the counter-electrode resistance.