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This review collects the most representative literature reports on the use of calix[4]arene-based molecules as components, namely photosensitizer dyes, in solar devices, including photovoltaics (dye-sensitized solar cells, DSSC), hydrogen photocatalytic and photoelectrochemical generation from water and sunlight, and CO2 photoreduction. Calix[4]arenes are versatile and easily obtainable scaffolds to be integrated with solar device molecular components either as electron-donor groups in π-conjugated dyes or as host-guest moieties to favor intermolecular interactions. Their beneficial role has been exploited to enhance photovoltaic, hydrogen production, and CO2 reduction performance, paving the way to a new class of molecular active components for next generation solar devices.

Dye-Sensitized Photoelectrochemical Cells (DS-PECs) have been emerging as promising devices for efficient solar-induced water splitting. In DS-PECs, dyes and catalysts for water oxidation and/or reduction are typically two separate components, thus limiting charge transfer efficiency. A small number of organometallic dyes have been integrated with a catalyst to form an integrated dye-catalyst dyad for photoanodes, but until now no dyads based on metal-free organic dyes have been reported for photoanodes. We herein report the first example of dyad-sensitized photoanodes in DS-PEC water splitting based on metal-free organic dyes and a Ru catalyst. The di-branched donor-π-acceptor dyes carry a donor carbazole moiety which has been functionalized with two different terminal pyridyl ligands in order to coordinate a benchmark Ru complex as a water oxidation catalyst, affording water oxidation dyads. The two dyads have been fully characterized in their optical and electrochemical properties, and XPS has been used to confirm the presence of the catalyst bonded to the dye anchored to the semiconductor anode. The two dyads have been investigated in DS-PEC, showing an excellent faradaic efficiency (88% average across all cells, with a best cell efficiency of 95%), thus triggering new perspectives for the design of efficient molecular dyads based on metal-free dyes for DS-PEC water splitting.

A series of functionalized ferrocene derivatives carrying electron-donor and electron-withdrawing (hetero)aromatic substituents has been designed as potential alternative electrolyte redox couples for dye-sensitized solar cells (DSSC). The compounds have been synthesized and fully characterized in their optical and electrochemical properties. A general synthetic approach that implies the use of a microwave assisted Suzuki coupling has been developed to access a significative number of compounds. The presence of different electron-rich and electron-poor substituents provided fine tuning of optical properties and energy levels. HOMO and LUMO energy values showed that the substitution of one or two cyclopentadienyl rings of ferrocene can be successfully exploited to increase the maximum attainable voltage from a standard DSSC device using TiO2 as a semiconductor, opening the way to highly efficient, non-toxic, and cheap redox shuttles to be employed in solar energy technologies.

We experimentally investigate the two-photon absorption cross sections and spectra of eosin and hematoxylin for applications in nonlinear microscopy. The experiments are carried out on pure samples of the two dyes in DI-water solvent with different concentrations, in the typical range employed in standard staining procedures. Nonlinear fluorescence is excited by a line-shaped beam emitted by a Ti:Sapphire mode-locked laser in the wavelength range from 740 to 880 nm and is detected through a microscope setup. The two-photon absorption spectral response is systematically analyzed and discussed. Finally, the staining is applied on biological tissue samples, which are imaged by two-photon microscopy. Our results show that the employed dyes are fully suitable for applications in nonlinear imaging.

Dye-sensitized solar cells containing sugar-based natural deep eutectic solvents (NADESs) as active electrolyte solvents have been studied in terms of their photovoltaic (PV) properties, including main PV characteristics, incident photon-to-current efficiency, and impedance properties. Five monosaccharides were selected as NADES H-bond donors and investigated with a phenothiazine-based sensitizer carrying a glucose functionality and a glucose-based co-adsorbent (glucuronic acid) to explore directional intermolecular interactions and to improve the PV performance. The highest power conversion efficiencies were recorded for cells containing the glucose-based sensitizer in the presence of glucuronic acid in the sugar-based NADES. When one of these components was omitted, performances were lower, suggesting that the best response came from an interplay between the sugar-based units. Not only has the unprecedented use of a NADES as a fully natural and bio-renewable dye-sensitized solar cell medium been presented, but for the first time an active role of the electrolyte solvent has been reported and exploited to increase the performance of the solar device.

Metal-free di-branched organic sensitizers, containing different heteroaromatic (phenothiazine, phenoxazine and carbazole) donor moieties, have been investigated as photoactive anode sensitizers in the photoelectrochemical generation of oxygen and water splitting. Photoelectrochemical properties have been studied both in the presence of a sacrificial electron donor, to closely evaluate the charge-transfer phenomena and the external quantum efficiency, and with a common water oxidation catalyst, to preliminarily assess the photoelectrochemical water-splitting activity and oxygen production. The experimental performance trend, in terms of photogenerated charge and evolved gas, was phenothiazine>carbazole>phenoxazine, arising from superior light-harvesting capability and more efficient electron injection to the semiconductor.

We report here the first example of a covalent functional nanocarbon hybrid based on a benchmark metal-free donor-π-acceptor (D-π-A) dye and reduced graphene oxide (RGO). The dyad, prepared by direct arylation of the RGO surface by means of an aniline derivative of the D-π-A species, has been thoroughly characterized in terms of dye loading percentage and spectroscopic properties, in comparison with the reference free dye, pristine RGO, and with an analogous non-covalent dye-RGO hybrid. When used as a photosensitizing agent in dye-sensitized solar cells (DSSC), the covalent hybrid demonstrated lower photovoltaic performances compared to the cell with the reference dye, a result that was mostly ascribed to the lower dye content of the former. Furthermore, the RGO based sensitizer showed stronger binding to the semiconductor oxide in comparison to the reference dye, paving the way to a new generation of DSSC photoanodes with improved chemical stability. This work demonstrates the full potential of the new class of hybrid sensitizers to equal or even exceed the photovoltaic performances achieved by standard organic photovoltaic sensitizers once molecular engineering of the functional nanocarbon hybrid has been refined.

Hybrid lead halide perovskites have been revolutionary in the photovoltaic research field, reaching efficiencies comparable with the most established photovoltaic technologies, although they have not yet reached their competitors&rsquo, stability. The search for a stable configuration requires the engineering of the charge extraction layers, in this work, molecular doping is used as an efficient method for small molecules and polymers employed as hole transport materials in a planar heterojunction configuration on compact-TiO2. We proved the viability of this approach, obtaining significantly increased performances and reduced hysteresis on compact titania-based devices. We investigated the photovoltaic performance correlated to the hole transport material structure. We have demonstrated that the molecular doping mechanism is more reliable than oxidative doping and have verified that molecular doping in polymeric hole transport materials leads to highly efficient perovskite solar cells, with long-term stability.

The synthesis, photophysical and electrochemical characterization, theoretical calculations and photovoltaic studies of a push-pull dye with an unconventional nonplanar tetrathiahelicene π−spacer between the donor-acceptor groups, are reported. The molecule exhibits suitable HOMO LUMO levels to be used in DSSC. The presence of the donor-acceptor helical architecture allows the internal charge transfer and subsequent electron injection to the conduction band of TiO2 leading to the good photocurrent value of 4.6 mA cm−2.

In this work, the data on the effect of peripheral functionalization of a series of triphenylamine based di-branched dyes used as sensitizers in dye-sensitized solar cells are presented. The effect of different alkyl functionalities on the donor moiety upon the optical and photovoltaics parameters have been investigated in dye-sensitized solar cells (DSSCs) using a 10-μm TiO2 active layer. The absorption spectra, output efficiency, and incident photon to conversion efficiency of the DSSCs have been collected. The data can be exploited for properly designing efficient, stable, and industrially viable dyes for third generation solar devices. Keywords: Photovoltaics, Renewable energies, Dye sensitized solar cells, Organic dyes

This review points out some of our recent advancements in dye-sensitized photocatalytic and photoelectrochemical hydrogen production. The dye sensitization of a semiconductor (SC) surface plays a central role. The dye has the task to improve the light harvesting of the system and guarantees a fast charge transfer to the SC, while avoiding charge recombination reactions that might reduce its efficiency. The introduction of different features and exploitation of molecular designs led to the development of twelve new dyes with a “push–pull” di-branched structure. The design of the molecular structure and geometry improves light harvesting, stability under long-term irradiation, and surface properties. The dyes have been investigated in a photocatalytic device, and then the most representative molecules have been studied also in photoelectrochemical cells (PEC), in the presence either of a sacrificial electron donor (SED), or of a water oxidation catalyst (WOC). The planar structure of the carbazole-based dye enhanced the photocatalytic hydrogen production activity almost tenfold compared to the phenothiazine derivative characterized by a butterfly-like structure; the latter was endowed with a better performance in the photoelectrochemical hydrogen production. Graphic abstract: [Figure not available: see fulltext.]

The data presented in this article are related to the research article entitled “An unconventional helical push-pull system for solar cells” (Dova et al., 2019). This article provides: a) the cyclic voltammogram plots in solution of helical push-pull sensitizers and the corresponding precursors; b) the visualization of the leading natural transition orbital (NTO) pairs obtained by theoretical calculation of frontiers orbitals; c) J/V curves of dye-sensitized solar cells (DSSC) sensitized by the dyes, without 3a,7a-dihydroxy-5b-cholic acid (CDCA) as co-adsorbent agent; d) 1H and 13C NMR spectra of dyes.

A new heteroarylene-vinylene donor-acceptor low bandgap polymer, the poly(DEHT-V-BTD), containing vinylene-spaced efficient donor (dialkoxythiophene) and acceptor (benzothiadiazole) moieties, is presented. Electropolymerization has been carried out by several electrochemical techniques and the results are compared. In particular, the pulsed potentiostatic method was able to provide layers with sufficient amounts of material. Cyclic voltammetries showed reversible behavior towards both p- and n-doping. The HOMO, LUMO, and bandgap energies were estimated to be -5.3, -3.6 and 1.8 eV, respectively. In situ UV-Vis measurements have established thatthe presence of the vinylene group stabilizes the formation of polaronic charge carriers even at high doping levels. © 2013 by the authors; licensee MDPI, Basel,Switzerland.

[Hybrid halide perovskite solar cells generally show differences in the power output depending on the voltage sweep direction, an undesired phenomenon termed hysteresis. Although the causes of this behavior have not yet been univocally determined, commonly, hysteresis heavily affects solar cells based on flat TiO2 as electron extracting layer. Herein, it is shown how perovskite material quality has a preeminent impact on hysteresis, and how combined deposition and post-deposition engineered manufacturing could lead to highly efficient and hysteresis-less solar cells, notwithstanding a planar TiO2-based layout. This methodology relies on solvent engineering during the casting process, leading to an ultra-flat, uniform, and thick film ensuring an optimal interface connection with the charge-extracting layer combined with post-deposition thermal and vacuum treatments, which merge the crystalline domains and cure the defects at the grain boundaries. This method allows obtaining perovskite active layer with superior optical properties, explaining the ideal device behavior and performances, therefore, a simple optimization of perovskite processing conditions can efficiently stem hysteresis targeting different device layouts. Power conversion efficiency of 15.4% and reduced hysteresis are achieved. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA., Weinheim.]

We report on the optical properties of polystyrene opals infiltrated with solutions of ad hoc synthesized heteroaromatic quadrupolar dyes endowed with strong nonlinear optical properties (two-photon absorption). Transmittance spectroscopy of opals infiltrated with dye water solutions shows both a bathochromic shift and a reduced width of the photonic crystal stop band. Moreover, variable angle transmittance spectra highlight the high energy dispersion of the stop band upon increasing the incidence angle. Photoluminescence spectra recorded at different emission angles with respect to the normal of the sample for such infiltrated opals show that the emission spectrum is strongly modified at the stop band according to the opal dispersion properties. A careful comparison of the intensity and spectral properties of photoluminescence in opals possessing a properly tuned photonic stop band is reported and discussed. Two different effects are observed: when concentrated solutions are used, emitted light filtering due to the photonic stop band is observed. On the other hand, by properly reducing solution self-absorption, directional enhancement of emission in the high energy side of the stop band is observed. Physical mechanisms responsible for this phenomenon are discussed. © 2010 American Chemical Society.

The first use of PSn-b-PEOm-b-PSn block copolymers (PS = polystyrene, PEO = poly(ethylene oxide)) as solid hosts for iodine/iodide electrolytes in dye-sensitized solar cells (DSSCs) is described. Using the benchmark photosensitizer N719, DSSC based on the quasi solid-state electrolytes afforded efficiencies up to 6.7%, to be compared with an efficiency of 7.3% obtained in similar conditions with a conventional iodine/iodide liquid electrolyte. By varying the PS:PEO relative volume ratio in the block copolymers different properties and morphologies were obtained. Copyright © 2013 Wiley Periodicals, Inc.

The amplification of Raman signals of the heteroaromatic cation 1-(N-methylpyrid-4-yl)-2-(N-methylpyrrol-2-yl)ethylene (PEP+)) bound to Au nanorods (NRs) was investigated at different excitation wavelengths to study the effect of the laser resonance with the absorption band of the PEP+ moiety and with the two plasmon oscillation modes of the NR. Two different PEP+ derivatives, differing in the length of the alkyl chain bearing the anchoring group, were used as target molecules. Raman spectra obtained exciting at 514 or at 785 nm (i.e., exciting the transverse or the longitudinal plasmon band) present a higher intensity than that at 488 nm suggesting a higher Raman amplification when the laser excitation wavelength is resonant with one of the two plasmon modes. Moreover, considering results of Discrete Dipole Approximation (DDA) calculations of the local field generated at the NR surface when either the transverse or the longitudinal plasmon modes are excited, we deduced that the resonance condition of the 514-nm laser excitation with the absorption band of the dye strongly contributes to the amplification of the Raman signal. © 2014 The Author(s).

A new heteroarylene-vinylene donor–acceptor polymer P(BDT-V-BTD) with reduced bandgap has been synthesized and its photophysical, electronic and photovoltaic properties investigated both experimentally and theoretically. The structure of the polymer comprises an unprecedented combination of a strong donor (4,8-dialkoxy-benzo[1,2-b:4,5-b']dithiophene, BDT), a strong acceptor (2,1,3-benzothiadiazole, BTD) and a vinylene spacer. The new polymer was obtained by a metal-catalyzed cross-coupling Stille reaction and fully characterized by NMR, UV–vis absorption, GPC, TGA, DSC and electrochemistry. Detailed ab initio computations with solvation effects have been performed for the monomer and model oligomers. The electrochemical investigation has ascertained the ambipolar character of the polymer and energetic values of HOMO, LUMO and bandgap matching materials-design rules for optimized organic photovoltaic devices. The HOMO and LUMO energies are consistently lower than those of previous heteroarylene-vinylene polymer while the introduction of the vinylene spacer afforded lower bandgaps compared to the analogous system P(BDT-BTD) with no spacer between the aromatic rings. These superior properties should allow for enhanced photovoltages and photocurrents in photovoltaic devices in combination with PCBM. Preliminary photovoltaic investigation afforded relatively modest power conversion efficiencies of 0.74% (AM 1.5G, 100 mW/cm2), albeit higher than that of previous heteroarylene-vinylene polymers and comparable to that of P(BDT-BTD). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

The first example of a heteroarylvinylene pi-conjugated quaterpyridine Ru(II) sensitizer (N1044) was synthesized and used in dye-sensitized solar cells; the dye has an effective panchromatic absorption band, covering the entire visible spectrum up to the NIR region, and superior electrochemical characteristics (HOMO/LUMO and bandgap energies) with respect to previous representative Ru(II) bi- and quaterpyridine sensitizers. A record IPCE curve ranging from 360 to 920 nm has been measured with a maximum of 65% at 646 nm and still 33% efficiency at 800 nm; this leads to substantially increased photocurrent (19.2 mA cm(-2)) when compared to the prototype N719 Ru(II) sensitizer.

We report on the preparation and optical characterization of three dimensional colloidal photonic crystal (PhC) containing an engineered planar defect embedding photoactive push-pull dyes. Free standing polystyrene films having thickness between 0.6 and 3 microns doped with different dipolar chromophores were prepared. These films were sandwiched between two artificial opals creating a PhC structure with planar defect. The system was characterized by reflectance at normal incidence angle (R), variable angle transmittance (T), and photoluminescence spectroscopy (PL). Clear evidence of defect states were observed in T and R spectra, which allow the light to propagate for selected frequencies within the pseudogap (stop band).