Acenaphthylene-Based Chromophores for Dye-Sensitized Solar Cells: Synthesis, Spectroscopic Properties, and Theoretical Calculations.

A set of acenaphthylene dyes with arylethynyl π-bridges was tested for dye-sensitized solar cells (DSSCs). Crucial steps for the extension of the conjugated system from the acenaphylene core involved Sonogashira coupling reactions. Phenyl, thiophene, benzotriazole, and thieno-[3,2-b]thiophene moieties were employed to extend the conjugation of the π-bridges. The systems were characterized by cyclic voltammetry and by UV-vis absorption and emission. The spectroscopic characterization showed that the last three bridges resulted in red-shifted absorption and emission spectra relative to the parent phenyl-bridged compound, in accordance with TD-DFT calculations. The phenylethynyl derivative 6a achieved a conversion efficiency of 2.51% with Voc, Jsc, and FF values of 0.365 V, 13.32 mA/cm2, and 0.52, respectively. The efficiency of this compound improved to 3.15% with the addition of CDCA (10 mM), representing the best efficiency result in this study. The overall conversion efficiency of the other aryl derivatives 6b-d proved to be significantly inferior (14-40%) to that of 6a due to a significant decrease of Jsc.

Comparing the Chemistry of Malvidin-3-O-glucoside and Malvidin-3,5-O-diglucoside Networks: A Holistic Approach to the Acidic and Basic Paradigms with Implications in Biological Studies.

The kinetics, thermodynamics, and degradation of malvidin mono- and diglucosides were studied following a holistic approach by extending to the basic medium. In acidic conditions, the reversible kinetics of the flavylium cation toward the equilibrium is controlled by the hydration and cis-trans isomerization steps, while in the basic medium, the OH- nucleophilic addition to the anionic quinoidal bases is the slowest step. There is a pH range (transition pHs), between the acidic and basic paradigms, that includes physiological pH (7.4), where degradation reactions occur faster, preventing the system from reaching the equilibrium. The transition pH of the diglucoside is narrower, and in contrast with the monoglucoside, there is no evidence for the formation of colored oligomers among the degradation products. Noteworthy, OH- addition in position 4 to form B42-, a kinetic product that decreases the overall equilibration rate, was observed only for the diglucoside.

Phototransduction in a supramolecular cascade: a mimic for essential features of the vision process.

The tailored design of a light-triggered supramolecular cascade results in an artificial machinery that assimilates the transduction of photons into chemical communication and the final release of a neurotransmitter. This is reminiscent of key steps in the natural vision process.

Intermolecular Copigmentation of Malvidin-3-O-glucoside with Caffeine in Water: The Effect of the Copigment on the pH-Dependent Reversible and Irreversible Processes.

Intermolecular copigmentation of malvidin-3-O-glucoside with caffeine was studied using a holistic procedure that includes the extension to basic pH values. In moderately basic solutions (7.5 < pH < 9.5) and independently of the copigment presence, there is a pH region where degradation of the quinoidal base and anionic quinoidal bases is faster than hydration and OH- nucleophilic addition, preventing the system from reaching the equilibrium. Intermolecular copigmentation with caffeine reduces significantly the degradation rate of quinoidal bases. In a more basic medium, the equilibrium is reached and degradation occurs from the anionic chalcones. In this case, the addition of caffeine also reduces the degradation rate in the interval 10 < pH < 11.5.

Modulating the thermodynamics, kinetics and photochemistry of 7-diethylamino-4'-dimethylaminoflavylium in water/ethanol, SDS and CTAB micelles.

The thermodynamics and kinetics of compound 7-diethylamino-4'-dimethylaminoflavylium were studied in water : ethanol (1 : 1) and water in the presence of SDS and CTAB micelles. The blue flavylium cation is in equilibrium with the pink protonated flavylium cation defined by pKAH2+/AH+ and the yellow trans-chalcone, defined by pKAH+/Ct. The difference between these two pKs gives the pH domain of the flavylium cation, ΔpK = 1.95 in CTAB, ΔpK = 5.6 in water/ethanol (1 : 1) and ΔpK = 8.5 in SDS micelles. On the other hand, the pH domain of the trans-chalcone is limited by pKAH+/Ct and pKCt/Ct-. It is lower in SDS micelles ΔpK = 2.7, increases in ethanol/water (1 : 1) ΔpK = 5.1 and is maximum in CTAB micelles, ΔpK = 6.8. All these effects can be explained by the electric charge present at the micellar surface. Relative energy level diagrams that allow for the explanation of the driving forces for any pH stimuli or light absorption were constructed from the calculated equilibrium constants. Irradiation of the trans-chalcone at 466 nm leads to the formation of the flavylium cation. In water : ethanol (1 : 1), the photochemistry is residual with Φ < 0.00002, while in SDS micelles at pH = 7 light increases the rate of the spontaneous conversion of trans-chalcone to the flavylium cation, with quantum yield Φ = 0.002; photochromism from trans-chalcone to give the flavylium cation with the same quantum yield is also observed in CTAB micelles.

Achieving Complexity at the Bottom: Molecular Metamorphosis Generated by Anthocyanins and Related Compounds.

The concept of molecular metamorphosis is described. A molecule (flavylium cation) generates a sequence of other different molecules by means of external stimuli. The reversibility of the system allows for the flavylium cation to be recovered by other external stimuli, completing one cycle. Differently from supramolecular chemistry, molecular metamorphosis is not a bottom-up approach. All events occur at the bottom. The procedures to characterize the kinetics and thermodynamics of the cycles are summarized. They are based on direct pH jumps (addition of a base to the flavylium cation) and reverse pH jumps (addition of an acid to equilibrated solutions at higher pH values). Stopped flow is an indispensable tool to characterize these systems. The following metamorphic cycles will be described to illustrate the concept: (i) introducing the flavanone in the metamorphic system and illustrating the concept of a timer at the molecular level; (ii) response of the flavylium-based metamorphosis to light inputs and the write-lock-read-unlock-erase molecular system; (iii) a one-way cycle of direct-reverse pH jumps; (iv) interconversion of the flavylium cation with 2,2'-spirobis[chromene] derivatives; (v) 6,8 A-ring substituent rearrangements.

A Transcriptomic Approach to the Metabolism of Tetrapyrrolic Photosensitizers in a Marine Annelid.

The past decade has seen growing interest in marine natural pigments for biotechnological applications. One of the most abundant classes of biological pigments is the tetrapyrroles, which are prized targets due their photodynamic properties; porphyrins are the best known examples of this group. Many animal porphyrinoids and other tetrapyrroles are produced through heme metabolic pathways, the best known of which are the bile pigments biliverdin and bilirubin. Eulalia is a marine Polychaeta characterized by its bright green coloration resulting from a remarkably wide range of greenish and yellowish tetrapyrroles, some of which have promising photodynamic properties. The present study combined metabolomics based on HPLC-DAD with RNA-seq transcriptomics to investigate the molecular pathways of porphyrinoid metabolism by comparing the worm's proboscis and epidermis, which display distinct pigmentation patterns. The results showed that pigments are endogenous and seemingly heme-derived. The worm possesses homologs in both organs for genes encoding enzymes involved in heme metabolism such as ALAD, FECH, UROS, and PPOX. However, the findings also indicate that variants of the canonical enzymes of the heme biosynthesis pathway can be species- and organ-specific. These differences between molecular networks contribute to explain not only the differential pigmentation patterns between organs, but also the worm's variety of novel endogenous tetrapyrrolic compounds.

New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations.

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 (λabs = 341 nm and λem = 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).

Light-Mediated Toxicity of Porphyrin-Like Pigments from a Marine Polychaeta.

Porphyrins and derivatives form one of the most abundant classes of biochromes. They result from the breakdown of heme and have crucial physiological functions. Bilins are well-known representatives of this group that, besides significant antioxidant and anti-mutagenic properties, are also photosensitizers for photodynamic therapies. Recently, we demonstrated that the Polychaeta Eulalia viridis, common in the Portuguese rocky intertidal, holds a high variety of novel greenish and yellowish porphyrinoid pigments, stored as granules in the chromocytes of several organs. On the follow-up of this study, we chemically characterized pigment extracts from the worm's skin and proboscis using HPLC and evaluated their light and dark toxicity in vivo and ex vivo using Daphnia and mussel gill tissue as models, respectively. The findings showed that the skin and proboscis have distinct patterns of hydrophilic or even amphiphilic porphyrinoids, with some substances in common. The combination of the two bioassays demonstrated that the extracts from the skin exert higher dark toxicity, whereas those from the proboscis rapidly exert light toxicity, then becoming exhausted. One particular yellow pigment that is highly abundant in the proboscis shows highly promising properties as a natural photosensitizer, revealing that porphyrinoids from marine invertebrates are important sources of these high-prized bioproducts.

Chemical evolution of the colour systems generated by riccionidin A, 3-deoxyanthocyanidins and anthocyanins.

The kinetics and thermodynamics (in acidic solutions) of the five chemical species reversibly interconnected by external stimuli (a multistate), such as pH and light, generated by the liverworts colorant riccionidin A were investigated. The degradation products of the multistate formed after 10 days at neutral pH were identified. The behaviour of riccionidin A multistate was compared with previous results reported for the equivalent systems based on 3-deoxyanthocyanidins (found in mosses and ferns) and anthocyanins (ubiquitous in angiosperms). The five chemical species have mutatis mutandis similar structures in the three multistates. The most dramatic difference is the extremely slow interconversion rate between flavylium cation and trans-chalcone in riccionidin A and related compounds multistates (tens of days) when compared with deoxyanthocyanins (a few days) and anthocyanins (several hours), at room temperature. The mole fraction distribution of the five species that constitute the multistate as a function of pH is also different in the three families of compounds. Some considerations regarding the chemical evolution of the three systems are given.

A Photoelectrochemical Study of Bioinspired 2-Styryl-1-Benzopyrylium Cations on TiO2 Nanoparticle Layer for Application in Dye-Sensitized Solar Cells.

In the present work, five 2-styryl-1-benzopyrylium salts and their relative self-assembly processes towards TiO2 nanocrystalline layers were evaluated as photosensitizers in dye-sensitized solar cells (DSSCs). Integration of these 2-styryl-1-benzopyrylium salts with the semiconductor allow for the performance of highly specific functions suitable for smart applications in material science. Spectroscopic and photoelectrochemical measurements conducted on these five bio-inspired dyes, in solution and upon adsorption onto titanium dioxide films, allowed detailed discussion of the anchoring ability of the different donor groups decorating the 2-styryl-1-benzopyrylium core and have demonstrated their ability as photosensitizers. Our results suggest that the introduction of a dimethylamino group in position 4' of the 2-styryl-1-benzopyrylium skeleton can alter the conjugation of the molecule leading to larger absorption in the visible region and a stronger electron injection of the dye into the conduction band of TiO2. Moreover, our experimental data have been supported by theoretical calculations with the aim to study the energy of the excited states of the five compounds. In this specific case, the simulations reported contributed to better describe the properties of the compounds used and to help create the necessary basis for the design of new and targeted bio-inspired molecules.

Ground and excited state properties of furanoflavylium derivatives.

The comparison of the ground-state reactivity of anthocyanins and aurone model compounds (i.e. with and without the furano bridge) has shown that the kinetic paradigm does not depend on the bridge but only on the hydroxyl substituent pattern, independently of the presence of the bridge: (i) bell shaped kinetics for those with two hydroxyl substituents in position 4' and 7, and (ii) four distinct kinetic steps for the mono substituted compounds with a hydroxyl in position 4'. The excited state proton transfer (ESPT) properties of these compounds were also investigated using steady-state and time-resolved spectroscopic techniques. It was found that the ESPT efficiency is significantly higher for the bridged compounds. Interestingly, pH-dependent steady-state fluorescence emission experiments show that in 4',7-dihydroxyfuranoflavylium the hydroxyl group in position 7 is the more acidic one in the excited state, while 1H NMR titration curves indicate a higher acidity constant in the ground state for the proton at the hydroxyl group in position 4'. Differently, the fluorescence emission spectrum of the quinoidal base deprotonated at position 7 is only observed upon excitation of the flavylium cation while the one from the base deprotonated at 4' is observed upon direct excitation.

pH-Dependent Multistate System Generated by a Synthetic Furanoflavylium Compound: An Ancestor of the Anthocyanin Multistate of Chemical Species.

The multistate of chemical species generated by 4'-hydroxy-3,2'-furanoflavylium is similar to that of anthocyanins and related compounds. This furanoflavylium multistate system was fully characterized by UV-visible and NMR spectroscopy, allowing determination of the respective equilibrium and rate constants. In contrast to the multistate generated by flavylium cations derived from anthocyanins and related compounds, the furanoflavylium multistate is characterized by much slower hydration and tautomerization (pyran ring opening-closing). In addition, the cis-trans isomerization of the chalcones of this system (2'-hydroxyaurones) is extremely slow when compared with anthocyanins. The observed similar order of magnitude for tautomerization and isomerization rate constants leads to peculiar kinetics from the flavylium cation (pH = 1) to the stable trans-chalcone (higher pH values). The hemiketal appears and disappears during the first stages of the kinetics, which gives the intermediate cis-chalcone (pseudo-equilibrium). This last species disappears in a much slower process, as fully characterized by 1H NMR, to give the final trans-chalcone.

Photo-controlled growth of polymeric submicron-sized particles.

A tripodal coumarin derivative shows complex photoreactivity, changing from intra- to intermolecular photodimerization with increasing concentration. At high concentration, the compound undergoes efficient photopolymerization, resulting in the formation of polymeric submicron-sized particles. The size of these particles can be precisely increased through photoirradiation, without affecting their polydispersity.

A Visible-Near-Infrared Light-Responsive Host-Guest Pair with Nanomolar Affinity in Water.

The discovery of stimuli-responsive high affinity host-guest pairs with potential applications under biologically relevant conditions is a challenging goal. This work reports a high-affinity 1:1 complex formed between cucurbit[8]uril and a water-soluble photochromic diarylethene derivative. It was found that, by confining the open isomer within the cavity of the receptor, a redshift in the absorption spectrum and an enhancement of the photocyclization quantum yield from Φ=0.04 to Φ=0.32 were induced. This improvement in the photochemical performance enables quantitative photocyclization with visible light that, together with the near-infrared light-induced ring-opening reaction and the 100-fold selectivity for the closed isomer, confirms this as an outstanding light-responsive affinity pair.

Thermodynamic Stability of Flavylium Salts as a Valuable Tool To Design the Synthesis of A-Type Proanthocyanidin Analogues.

A convenient method to synthesize A-type proanthocyanidin analogues from flavylium salts and π-nucleophiles has been developed. It was found that the thermodynamic stability of the starting flavylium salt, assessed by the measurement of the apparent acidity constant ( K'a), was the key parameter to design effective one-pot reactions between flavylium salts and nucleophiles such as phloroglucinol and (+)-catechin. When flavylium salts have a p K'a value of 1.7 or lower, the synthesis of the corresponding 2,8-dioxabyciclo[3.3.1]nonane derivative was properly achieved.

Incorporation of Coumarin-Based Fluorescent Monomers into Co-Oligomeric Molecules.

With the purpose of modifying organic fluorescent dyes based on the coumarin scaffold, and developing and evaluating a route to its incorporation into a polymeric backbone, a study was conducted on the co-polymerization of 3-vinylcoumarins with styrene and methyl acrylate using 2,2-azobis(isobutyronitrile) (AIBN) as the radical initiator. The structural and photophysical characterization proved the incorporation of the coumarin monomers into the polymeric chain and further showed a decrease in the fluorescence quantum yields in the co-oligomers.

Achieving Complexity at the Bottom. 2,6-Bis(arylidene)cyclohexanones and Anthocyanins: The Same General Multistate of Species.

As in supramolecular chemistry, complexity could also be achieved through a bottom-up approach. Anthocyanins and related compounds such as the compound (E)-6-(dimethylamino)-4-(4-(dimethylamino)-2-hydroxybenzylidene)-1,2,3,4-tetrahydroxanthylium chloride (1), here reported, exhibit this type of complexity. The thermodynamics and kinetics of the complex multistate of species of compound 1 were studied by conventional and stopped-flow UV-visible spectrophotometry as well as by NMR. The system follows the same multistate of species of anthocyanins, except for the presence at moderately basic pH values of a species possessing a spiro carbon. The introduction of two dimethylamino substituents in positions 4' and 7, modulates deeply the thermodynamic and kinetics of the system. A beautiful pH-dependent palette of colors is obtained, including a blue flavylium cation at unusually high pH values. The protonation of the dimethylamino substituents is the key aspect for explaining the details of the spiro opening kinetics. The system was fully characterized by representing the mole fraction distribution and the relative energy level diagram of all multistate species as a function of pH.

pH-Driven self-sorting in a four component host-guest system.

A four component host-guest system comprising ß-cyclodextrin (ß-CD), cucurbit[7]uril (CB7) and two chalcone guests was demonstrated to undergo pH-triggered self-sorting in aqueous solution. This phenomenon arises from the contrasting complexation induced pKa shifts displayed by these guests after complexation with CB7.

2,2'-Spirobis[chromene] Derivatives Chemistry and Their Relation with the Multistate System of Anthocyanins.

The chemistry of 2,2'-spirobis[chromene] derivatives is intimately related to the one of anthocyanins and similar compounds. The 2,2'-spirobis[chromene] species plays a central role in the network of chemical reactions connecting two different flavylium-based multistate systems. In the present work, a new asymmetric 2,2'-spirobis[chromene] intermediate possessing a constrained propylenic bridge between carbons 3 and 3' was isolated and its role as a pivot in the anthocyanins-type multistate of chemical reactions was investigated by the conjugation of absorption spectroscopy, stopped-flow, NMR, and X-ray crystallography. It was confirmed that the propylenic bridge is essential to stabilize the spirobis[chromene] species. Furthermore, under acidic conditions, two cis-trans styrylflavylium isomers were identified, which could be interconverted directly into one another with light. This is the first report of styrylflavylium cations with photoisomerization on the styryl moiety.