The Versatile Photo-Thermal Behaviour of a 2-Hydroxyazobenzene.

Photochromic compounds are employed in implementing neuron surrogates. They will boost the development of neuromorphic engineering in wetware. In this work, the photochromic behaviours of (E)-3,4,6-trichloro-2-(p-diazenil)-phenol (t-DZH) and its conjugated phenoxide base (t-DZ) have been investigated experimentally in three different media: (1) pure acetonitrile, (2) in water and acetonitrile mixed in a 1/1 volume ratio, and (3) in an aqueous micellar solution of 3-(N,N-Dimethylmyristylammonio)propanesulfonate (SB3-14). The analysis of the spectral and kinetic features of t-DZH and t-DZ has been supported by quantum-mechanical DFT calculations, the maximum entropy method, and the determination of their colourability (C). The versatility of t-DZH and t-DZ makes them promising molecular probes of micro-environments and potential ingredients of photochemical oscillators required for implementing pacemaker neurons capable of communicating through optical signals in wetware.

Modelling the Interaction between Carboxylic Acids and Zinc Oxide: Insight into Degradation of ZnO Pigments.

Computational modelling applied to cultural heritage can assist the characterization of painting materials and help to understand their intrinsic and external degradation processes. The degradation of the widely employed zinc oxide (ZnO)-a white pigment mostly used in oil paints-leads to the formation of metal soaps, complexes of Zn ions and long-chain fatty acids coming from the degradation of the oil binder. Being a serious problem affecting the appearance and the structural integrity of many oil paintings, it is relevant to characterize the structure of these complexes and to understand the reaction pathways associated with this degradation process. Density functional theory (DFT) calculations were performed to investigate the adsorption of the acetate and acetic acid on relatively large ZnO clusters and the formation of Zn-acetate complexes. Carboxylic acids with longer alkyl chains were then investigated as more realistic models of the fatty acids present in the oil medium. In addition, DFT calculations using a periodic ZnO slab were performed in order to compare the obtained results at different levels of theory. Optimization calculations as well as the formation energies of the ZnO@carboxylate coupled systems and the thermodynamics leading to possible degradation products were computed. Our results highlight the potential for DFT calculations to provide a better understanding of oil paint degradation, with the aim of contributing to the development of strengthening and conservation strategies of paintings.

Towards efficient sustainable full-copper dye-sensitized solar cells.

Two new heteroleptic copper(i) sensitizers bearing 6,6'-dimethyl-2,2'-bipyridine-4,4'-dibenzoic acid, to anchor the dye on the titania surface, and a π-delocalized 2-(R-phenyl)-1H-phenanthro[9,10-d]imidazole (R = NPh2 or O-hexyl) ancillary ligand were prepared and well characterized. Their performance as dyes in DSSCs is quite similar to that of the related complex bearing 2,9-dimesityl-1,10-phenanthroline as an ancillary ligand, when using the common I-/I3- redox couple or homoleptic copper complexes as electron shuttles. The experimental results along with theoretical calculations confirm the great potential of full-copper DSSCs.

Novel cyclometallated 5-π-delocalized donor-1,3-di(2-pyridyl)benzene platinum(ii) complexes with good second-order nonlinear optical properties.

Five new platinum(ii) complexes bearing a cyclometallated 5-π-delocalized donor-1,3-di(2-pyridyl)benzene were prepared and fully characterized. Their second-order nonlinear optical (NLO) properties were determined by the Electric-Field Induced Second Harmonic generation (EFISH) technique, working in DMF solution with an incident wavelength of 1907 nm, whereas the dipole moments were determined by Density Functional Theory (DFT) calculations. Remarkably, the platinum(ii) complex with a cyclometallated 5-guaiazulene-CH[double bond, length as m-dash]CH-1,3-di(2-pyridyl)benzene appears as a very good candidate for application in photonics, being characterized by the largest second-order NLO response. Besides, it appeared that the nature of substituents on thiophene, chosen as π-delocalized moiety in position 5 of the 1,3-di(2-pyridyl)benzene, strongly affects the NLO properties.

Photochemistry of Artists' Dyes and Pigments: Towards Better Understanding and Prevention of Colour Change in Works of Art.

The absorption of light gives a pigment its colour and its reason for being, but it also creates excited states, that is, new molecules with an energy excess that can be dissipated through degradation pathways. Photodegradation processes provoke long-term, cumulative and irreversible colour changes (fading, darkening, blanching) of which the prediction and prevention are challenging tasks. Of all the environmental risks that affect heritage materials, light exposure is the only one that cannot be controlled without any impact on the optimal display of the exhibit. Light-induced alterations are not only associated with the pigment itself but also with its interactions with support/binder and, in turn, are further complicated by the nature of the environmental conditions. In this Minireview we investigate how chemistry, encompassing multi-scale analytical investigations of works of art, computational modelling and physical and chemical studies contributes to improve our prediction of artwork appearance before degradation and to establish effective preventive conservation strategies.

Designing Squaraines to Control Charge Injection and Recombination Processes in NiO-based Dye-Sensitized Solar Cells.

Herein, the synthesis of a new family of squaraines (SQs) and their application in p-type dye-sensitized solar cells (DSSCs) is presented. In particular, two sets of SQs were designed featuring either two or four anchoring carboxylic groups combined with either oxygen or dicyanovinyl central groups. The SQs were characterized by using a joint theoretical, photophysical, and electrochemical approach. Importantly, the presence of different central groups forces a frozen cis (dicyanovinyl group) or a trans (oxygen group) SQ conformation. Based on the latter, the current work enables a direct comparison between cis and trans isomers as well as the impact of a different number of anchors. Considering their electron-accepting and light-harvesting character, they were tested in NiO-based DSSCs. Photocurrent-voltage, incident photon-to-current conversion efficiency (IPCE), and electrochemical impedance spectroscopy measurements were performed. By virtue of their different symmetry, stereochemistry, and number of carboxylic groups, altered adsorption behavior onto NiO electrodes as well as diverse charge injection and charge recombination dynamics were noted under operation conditions. SQs with four linkers in a frozen cis isomerism show the best charge collection properties among the investigated SQs, providing a valuable guideline for the molecular design of future SQs for p-type DSSCs. In addition, we assembled tandem DSSCs featuring SQ/NiO photocathodes and N719/TiO2 photoanodes. The IPCE of the resulting tandem DSSCs implies light harvesting throughout most of the visible part of the solar spectrum owing to the complementary absorption features of SQ and N719.

Tuning the dipolar second-order nonlinear optical properties of 5-π-delocalized-donor-1,3-di(2-pyridyl)benzenes, related cyclometallated platinum(ii) complexes and methylated salts.

The synthesis and characterization of three 5-π-delocalized-donor-1,3-di(2-pyridyl)benzenes is reported along with that of their related cyclometallated platinum(ii) complexes and N,N-dimethylated iodide salts. The second-order nonlinear optical (NLO) properties of all the compounds have been determined by the Electric Field Induced Second Harmonic generation technique, showing how the µßEFISH absolute value of 1,3-di(2-pyridyl)benzenes can be tuned by the nature of the substituent on position 5 of the central benzene ring, and greatly increased by cyclometallation to Pt or by N-methylation.

From Blue to Green: Fine-Tuning of Photoluminescence and Electrochemiluminescence in Bifunctional Organic Dyes.

We describe the synthesis, computational analysis, photophysics, electrochemistry and electrochemiluminescence (ECL) of a series of compounds formed of two triphenylamines linked by a fluorene or spirobifluorene bridge. The phenylamine moieties were modified at the para-position of the two external rings by electron-withdrawing or electron-donating substituents. These modifications allowed for fine-tuning of the photoluminescence (PL) and ECL emission from blue to green, with an overall wavelength span of 73 (PL) and 67 (ECL) nm, respectively. For all compounds, we observed a very high PL quantum yield (79-89%) and formation of stable radical ions. The ECL properties were investigated by direct annihilation of the electrogenerated radical anion and radical cation. The radical-ion annihilation process is very efficient and causes an intense greenish-blue ECL emission, easily observable even by naked eye, with quantum yield higher than the standard 9,10-diphenylanthracene. The ECL spectra show one single band that almost matches the PL band. Because the energy of the annihilation reaction is higher than that required to form the singlet excited state, the S-route is considered the favored pathway followed by the ECL process in these molecules. All these features point to this type of molecular system as promising for ECL applications.

Geometrical and energetical structural changes in organic dyes for dye-sensitized solar cells probed using photoelectron spectroscopy and DFT.

The effects of alkoxy chain length in triarylamine based donor-acceptor organic dyes are investigated with respect to the electronic and molecular surface structures on the performance of solar cells and the electron lifetime. The dyes were investigated when adsorbed on TiO2 in a configuration that can be used for dye-sensitized solar cells (DSCs). Specifically, the two dyes D35 and D45 were compared using photoelectron spectroscopy (PES) and density functional theory (DFT) calculations. The differences in solar cell characteristics when longer alkoxy chains are introduced in the dye donor unit are attributed to geometrical changes in dye packing while only minor differences were observed in the electronic structure. A higher dye load was observed for D45 on TiO2. However, D35 based solar cells result in higher photocurrent although the dye load is lower. This is explained by different geometrical structures of the dyes on the surface.

DFT/TDDFT investigation on the UV-vis absorption and fluorescence properties of alizarin dye.

The photophysical and photochemical properties of alizarin, a fluorescent organic red dye of the family of the anthraquinones, have been theoretically investigated by focusing our attention on its emission properties in relation to an excited-state internal proton transfers from the phenolic hydroxyl group to the carbonyl oxygen. The potential energy curve of the proton transfer in the first excited state has been computed in solvents of different polarity and the emission spectra of both tautomers simulated, including the vibronic effects, using the Franck-Condon approximation. Calculations performed by equilibrating the solvent with the excited-state geometry and electron density using a self-consistent procedure have led to interesting differences with respect to their linear response counterpart. The results obtained point out that, while the emission energy of alizarin is sensitive to solvent polarity, that of the proton-transfer tautomer is computed at similar wavelengths independently of the solvent. Comparison between computed and experimental data has allowed us to rationalize the alizarin double emission measured in non-polar solvents.

Electronic and optical properties of dye-sensitized TiO2 interfaces.

Dye-sensitized solar cells (DSCs) represent a promising approach to the direct conversion of sunlight to electrical energy at low cost and high efficiency. DSCs are based on a film of anatase TiO2 nanoparticles covered by adsorbed molecular dyes and immersed in a liquid redox electrolyte. Upon photoexcitation of the chemisorbed dye, electrons are injected into the TiO2 conduction band and can travel across the nanostructured film to reach the counter-electrode, while the oxidized dye is regenerated by the redox electrolyte. In this review we present a summary of recent computational studies of the electronic and optical properties of dye-sensitized TiO2 interfaces, with the aim of providing the basic understanding of the operation principles of DSCs and establishing the conceptual basis for their design and optimization.We start with a discussion of isolated dyes in solution, focusing on the dye's atomic structure, ground and excited state oxidation potentials, and optical absorption spectra. We examine both Ru(II)-polypyridyl complexes and organic "push-pull" dyes with a D-π-A structure, where the donor group (D) is an electron-rich unit, linked through a conjugated linker (π) to the electron-acceptor group (A). We show that a properly calibrated computational approach based on Density Functional Theory (DFT) combined with Time Dependent DFT (TD-DFT) can provide a good description of both the absorption spectra and ground and excited state oxidation potential values of the Ru(II) complexes. On the other hand, organic push-pull dyes are not well described by the standard DFT/TD-DFT approach. For these dyes, an excellent description of the electronic structure in gas phase can be obtained by the many body perturbation theory GW method, which has, however, a much higher computational cost.We next consider interacting dye/semiconductor systems. Key properties are the dye adsorption structure onto the semiconductor, the nature and localization of the dye@semiconductor excited states, and the alignment of ground and excited state energy levels at the dye/semiconductor heterointerface. These properties, along with an estimate of the electronic coupling, constitute the fundamental parameters that determine the electron injection and dye regeneration processes. For metallorganic dyes, standard DFT/TDDFT methods are again found to reproduce accurately most of the relevant electronic and optical properties. For highly conjugated organic dyes, characterized by a high degree of charge transfer excited states, instead, the problems associated to the charge-transfer nature of their excited states extend to their interaction with TiO2 and translate into an erroneous description of the relative energetics of dye/semiconductor excited states. A full description of push-pull organic dyes/semiconductor excited states, which is essential for modeling the key process of electron injection in DSCs, still represents a challenge which should be addressed by next generation DFT or post-DFT methods.

Impact of Spin-Orbit Coupling on Photocurrent Generation in Ruthenium Dye-Sensitized Solar Cells.

Relativistic TDDFT calculations have been performed employing a novel computational approach to evaluate the impact of spin-orbit coupling (SOC) in the optical and photovoltaic properties of panchromatic Ru(II) dyes for dye-sensitized solar cells (DSCs). The employed computational setup accurately reproduces the optical properties of the investigated dyes, allowing an assessment of the factors responsible for the varying SOC with the dye metal-ligand environment. While for the prototypical panchromatic black dye sensitizer a negligible SOC effect is found, the SOC-induced spectral broadening calculated for the recently reported DX1 dye partly enhances the light-harvesting efficiency and consequently the photocurrent generation in DSCs based on this dye.

A simple synthetic route to obtain pure trans-ruthenium(II) complexes for dye-sensitized solar cell applications.

We report a facile synthetic route to obtain functionalized quaterpyridine ligand and its trans-dithiocyanato ruthenium complex, based on a microwave-assisted procedure. The ruthenium complex has been purified using a silica chromatographic column by protecting carboxylic acid groups as iso-butyl ester, which are subsequently hydrolyzed. The highly pure complex exhibits panchromatic response throughout the visible region. DFT/time-dependent DFT calculations have been performed on the ruthenium complex in solution and adsorbed onto TiO2 to analyze relative electronic and optical properties. The ruthenium complex endowed with the functionalized quaterpyridine ligand was used as a sensitizer in dye-sensitized solar cell yielding a short-circuit photocurrent density of more than 19 mA cm(-2) with a broad incident photon to current conversion efficiency spectra ranging from 400 to 900 nm, exceeding 80 % at 700 nm.

Protic ionic liquids as p-dopant for organic hole transporting materials and their application in high efficiency hybrid solar cells.

Chemical doping is a powerful method to improve the charge transport and to control the conductivity in organic semiconductors (OSs) for a wide range of electronic devices. We demonstrate protic ionic liquids (PILs) as effective p-dopant in both polymeric and small molecule OSs. In particular, we show that PILs promote single electron oxidation, which increases the hole concentration in the semiconducting film. The illustrated PIL-doping mechanism is compatible with materials processed by solution and is stable in air. We report the use of PIL-doping in hybrid solar cells based on triarylamine hole transporting materials, such as 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). We show improved power conversion efficiency by replacing lithium salts, typical p-dopants for spiro-OMeTAD, with PILs. We use photovoltage-photocurrent decay and photoinduced absorption spectroscopy to establish that significantly improved device performance is mainly due to reduced charge transport resistance in the hole-transporting layer, as potentiated by PIL-doping.

Tuning the dipolar second-order nonlinear optical properties of cyclometalated platinum(II) complexes with tridentate N

Appropriate functionalization of the cyclometalated ligand, L, and the choice of the ancillary ligand, X, allows the dipolar second-order nonlinear optical response of luminescent [PtLX] complexes--in which L is an N^C^N-coordinated 1,3-di(2-pyridyl)benzene ligand and X is a monodentate halide or acetylide ligand--to be controlled. The complementary use of electric-field-induced second-harmonic (EFISH) generation and harmonic light scattering (HLS) measurements demonstrates how the quadratic hyperpolarizability of this appealing family of multifunctional chromophores, characterized by a good transparency throughout much of the visible region, is dominated by an octupolar contribution.

Role of hot singlet excited states in charge generation at the black dye/TiO2 interface.

Photoinduced electron transfer at low-band-gap ruthenium-based dye/TiO2 has been investigated by means of ultrafast transient absorption and DFT/TDDFT calculations. We demonstrate that although the charge generation mechanism is triplet mediated upon band gap excitation, as already proven in high band gap dyes such as the well-known N3 and N719, when excess energy is provided which allows to reach high energy singlet states still in the visible spectral range, ultrafast electron transfer takes place. No intersystem crossing process is observed and charge generation happens only from the singlet excited state.

Everything you always wanted to know about black dye (but were afraid to ask): a DFT/TDDFT investigation.

We report an exhaustive theoretical and computational investigation of the electronic, optical, redox and acid-base properties, along with the adsorption mode on TiO2, of Black Dye (BD), the prototypical panchromatic dye for solar cell applications. We investigated in detail the variation of the relevant dye properties as a function of the solution pH, corresponding to the stepwise deprotonation of the carboxylic groups. Our results reproduced the expected blue-shift of the optical absorption spectrum and the experimental trend of oxidation potentials by increasing pH, which turned both out to be in excellent agreement with experimental values. Also, our calculated excited state oxidation potential is in good agreement with available experimental data. We then looked at the pKa of the various deprotonation steps, finding lowest pKa values for the stepwise dissociation of three protons of 2.71, 3.69 and 5.20, in excellent agreement with experimental pKa values of 3 and 5, for two and one protons dissociation, respectively. We finally investigated the adsorption of BD on TiO2, finding the most stable adsorption to occur via two dissociated monodentate carboxylic groups. Inspection of the electronic structure and alignment of energy levels for N719 and BD revealed a reduced driving force for electron injection in the latter dye, which could possibly lead to energetically unfavorable electron transfer from the excited dye to the TiO2 conduction band. Our results may constitute a reference study for future investigations and optimization of BD-based dye-sensitized solar cells.

An investigation on the second order nonlinear optical response of tris-cyclometallated Ir(III) complexes with variously substituted 2-phenylpyridines.

The second order nonlinear optical (NLO) properties of various simple tris-cyclometallated Ir(III) complexes bearing 2-phenylpyridine ligands have been investigated by means of the EFISH technique, evidencing how appropriate substitution of the cyclometallated ligands may allow the tuning of the second-order NLO response of this unusual family of 3D chromophores. To evaluate the dipole moments and to gain insight into the electronic structure and optical properties of the investigated complexes we also performed Density Functional Theory (DFT) calculations.

New [(D-terpyridine)-Ru-(D or A-terpyridine)][4-EtPhCO2]2 complexes (D = electron donor group; A = electron acceptor group) as active second-order non linear optical chromophores.

The dipolar and octupolar contributions of the second order nonlinear optical properties of [(4'-(C(6)H(4)-p-D)-2,2':6',2''-terpyridine)-Ru-(4'-(C(6)H(4)-p-A)-2,2':6',2''-terpyridine)]Y(2) heteroleptic complexes (D and A are donor and acceptor groups, respectively), and related free terpyridines and homoleptic complexes, have been obtained by means of a comprehensive combination of Electric Field Induced Second Harmonic generation, Third Harmonic Generation, and Harmonic Light Scattering measurements. These results evidence how a metal can act as a bridge between two π-delocalized terpyridine moieties bearing a D and an A group, respectively, leading to a large quadratic hyperpolarizability hugely dominated by the octupolar contribution.