Conformational and environmental effects on the electronic and vibrational properties of dyes for solar cell devices.

The main challenge for solar cell devices is harvesting photons beyond the visible by reaching the red-edge (650-780 nm). Dye-sensitized solar cell (DSSC) devices combine the optical absorption and the charge separation processes by the association of a sensitizer as a light-absorbing material (dye molecules, whose absorption can be tuned and designed) with a wide band gap nanostructured semiconductor. Conformational and environmental effects (i.e., solvent, pH) can drastically influence the photophysical properties of molecular dyes. This study proposes a combined experimental and computational approach for the comprehensive investigation of the electronic and vibrational properties of a unique class of organic dye compounds belonging to the family of red-absorbing dyes, known as squaraines. Our focus lies on elucidating the intricate interplay between the molecular structure, vibrational dynamics, and optical properties of squaraines using state-of-the-art density functional theory calculations and spectroscopic techniques. Through systematic vibrational and optical analyses, we show that (i) the main absorption peak in the visible range is influenced by the conformational and protonation equilibria, (ii) the solvent polarity tunes the position of the UV-vis absorption, and (iii) the vibrational spectroscopy techniques (infrared and Raman) can be used as informative tools to distinguish between different conformations and protonation states. This comprehensive understanding offers valuable insights into the design and optimization of squaraine-based DSSCs for enhanced solar energy conversion efficiency.

Chalcogen atom effect on the intersystem crossing kinetic constant of oxygen- and sulfur disubstituted heteroporphyrins.

The modulation of the photophysical properties of di-substituted porphyrin rings upon the oxygen and sulfur-for-nitrogen replacement has been investigated at density functional theory (DFT) and its time-dependent formulation (TDDFT). The considered properties range from structural behaviors and excitation energies to spin-orbit coupling (SOC) and nonradiative intersystem kinetic constants. Results show that the SOC strongly increase upon chalcogen substitution and, accordingly, the computed nonradiative kinetic constant also indicate an efficient singlet-triplet intersystem crossing in the sulfur containing macrocycle. The presented results indicate an alternative way to properly modulate the porphyrin's crucial properties for their use in photodynamic therapy, without resorting to the use of heavy atoms.

On the antibacterial photodynamic inactivation mechanism of Emodin and Dermocybin natural photosensitizers: A theoretical investigation.

A DFT and TDDFT study has been carried out on monomeric anthraquinones Emodin and Dermocybin (Em, Derm) recently proposed as natural antibacterial photosensitizers able to act also against gram-negative microbes. The computational study has been performed considering the relative amount of neutral and ionic forms of each compound in water, with the variation of pH. The occurrence of both Type I and Type II photoreactions has been explored computing the absorption properties of each species, the spin-orbit coupling constants (SOC), the vertical ionization potentials and the vertical electron affinities. The most plausible deactivation channels leading to the population of excited triplet states have been proposed. Our data indicate Emodin as more active than Dermocybin in antimicrobial photodynamic therapy throughout the Type II mechanism. Our data support a dual TypeI/II activity of the monomeric anthraquinones Emodin and Dermccybin in water, in all the considered protonation states.

Sulphur- and Selenium-for-Oxygen Replacement as a Strategy to Obtain Dual Type I/Type II Photosensitizers for Photodynamic Therapy.

The effect on the photophysical properties of sulfur- and selenium-for-oxygen replacement in the skeleton of the oxo-4-dimethylaminonaphthalimide molecule (DMNP) has been explored at the density functional (DFT) level of theory. Structural parameters, excitation energies, singlet-triplet energy gaps (ΔES-T), and spin-orbit coupling constants (SOC) have been computed. The determined SOCs indicate an enhanced probability of intersystem crossing (ISC) in both the thio- and seleno-derivatives (SDMNP and SeDMNP, respectively) and, consequently, an enhancement of the singlet oxygen quantum yields. Inspection of Type I reactions reveals that the electron transfer mechanisms leading to the generation of superoxide is feasible for all the compounds, suggesting a dual Type I/Type II activity.

Chalcogen Effects in the Photophysical Properties of Dimethylamino-1,8-naphthalimide Dyes Revealed by DFT Investigation.

Thionation of carbonyl groups of known dyes is a rapidly emerging strategy to propose an advance toward heavy-atom-free photosensitizers to be used in photodynamic therapy (PDT). The sulfur-for-oxygen replacement has recently proved to enhance the singlet oxygen quantum yield of some existing fluorophores and to shift the absorption band at longer wavelengths. Drawing inspiration from this challenging evidence, the effect of both sulfur- and selenium-for-oxygen replacement in the skeleton of the oxo-4-dimethylamino-1,8-naphthalimide molecule (DMN) has been analyzed by means of a DFT study. The thio- and seleno-derivatives (SDMN and SeDMN, respectively) have been shown to offer the possibility to access a multitude of ISC (intersystem crossing) pathways involved in the triplet deactivation mechanisms with a consequent enhancement of the singlet oxygen production, also arising from the change of orbital type involved in the radiationless 1nπ* → 3ππ* transitions. Moreover, the change in nature from a 1ππ* to a 1nπ* observed in the SeDMN has been revealed to be crucial to reach more clinically useful regions of the spectrum suggesting that the selenium-for-oxygen replacement can be proposed as a strategy to achieve more suitable PDT agents while proposing an advance toward heavy-atom-free PSs.

The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes.

In this review, we provide a brief overview of the contribution that computational studies can offer to the elucidation of the electronic mechanisms responsible for the electrochromism phenomenon, through the use of the density functional theory (DFT) and its time-dependent formulation (TDDFT). Although computational studies on electrochromic systems are not as numerous as those for other physico-chemical processes, we will show their reliability and ability to predict structures, excitation energies, and redox potentials. The results confirm that these methods not only help in the interpretation of experimental data but can also be used for the rational design of molecules with interesting electrochromic properties to be initiated for synthesis and experimental characterization.

Photophysical properties of heavy atom containing tetrasulfonyl phthalocyanines as possible photosensitizers in photodynamic therapy.

The excitation energies, singlet-triplet energy gap and spin-orbit coupling constants for Zn-, GaCl-, Pd-, and Pt- tetrasulfonyl phthalocyanines complexes (ZnPc, GaClPc, PdPc, and PtPc) have been computed by using the density functional theory and employing the M06 exchange-correlation functional. Results show that these systems possess interesting photophysical properties, which make them possible photosensitizers to be proposed in photodynamic therapy (PDT). Absorption energies of all the complexes examined have been found falling inside the so-called therapeutic window (550-800 nm). Singlet-triplet energy gap values are higher than those required for the production of cytotoxic molecular oxygen and the spin-orbit coupling constants are such as to ensure an efficient spin orbit intersystem crossing. The obtained data are consistent with the experimental oxygen singlet quantum yields. The platinum complex appears to be the most effective candidate to propose for PDT.

Theoretical exploration of the photophysical properties of two-component RuII-porphyrin dyes as promising assemblies for a combined antitumor effect.

Due to the extraordinary success of porphyrins in photodynamic therapy (PDT) and Ru compounds as chemotherapeutics, a series of RuII-porphyrin complexes have recently been synthesized and proposed as promising dual-action therapeutic agents. The results of a careful DFT and TDDFT investigation on four mononuclear pyridyl triphenylporphyrin RuII-arene complexes are herein reported and compared with those obtained for the metal-free derivatives. The investigation aims at shedding light on the modulation of the photophysical properties of the light absorber upon metalation and exploring the hydrolysis process of the RuII-moiety in the presence of the bulky porphyrin unit. Type I and Type II photoreactions were analyzed computing absorption spectra, singlet-triplet energy gaps, spin orbit coupling constants and vertical electron affinity (VEA) along with ionization potentials (VIP) for all the investigated compounds, while the chloride/water exchange reaction kinetics were determined by exploring the first and second aquation reactions of the Ru-moiety. Despite the highly similar photophysical properties displayed by the members of this class of compounds, an analysis of the hydrolysis processes in the dark allows to point out an interesting difference related to the type of pyridylporphyrin isomer and could be a preliminary explanation of the greater phototoxicity experimentally found for 3'-pyridyl substituted compounds.

Iodine substituted phosphorus corrole complexes as possible photosensitizers in photodynamic therapy: Insights from theory.

The search for new dyes to be used as photosensitizers in photodynamic therapy (PDT) is a field of great interest from both experimental and theoretical viewpoints. In this study, the main photophysical properties (excitation energies, singlet-triplet energy gap, and spin orbit coupling matrix elements) of some unsubstituted and iodine substituted phosphorus corrole complexes have been determined by using density functional theory and its time-dependent formulation. Results show that these compounds can be proposed as photosensitizers in PDT. The heavy atom effects have been rationalized on the basis of El-Sayed rules.

Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes.

The conversion reaction of NO to NO3- ion catalyzed by the end-on [Cr(III)(n-TMC)(O2)(Cl)]+ superoxo and side-on [Cr(IV)(n-TMC)(O2)(Cl)]+ peroxo non-heme complexes (n = 12, 13, 14 and 15), which are biomimetic systems of nitric oxide dioxygenases (NODs), has been explored using a computational protocol in the framework of density functional theory. Results show that the potential energy profiles for the studied reactions lie above the reagent energies, regardless of the used catalyst. Both the O-O bond breaking in the biomimetics and the NO3- ion formation require low energy barriers suggesting an efficient catalytic power of the studied systems. The rate-determining step depends on ligand size.

Rational Design of Modified Oxobacteriochlorins as Potential Photodynamic Therapy Photosensitizers.

The modulation of the photophysical properties of a series of recently synthetized oxobacteriochlorins with the introduction of heavy atoms in the macrocycles, was investigated at density functional level of theory and by means of the time-dependent TDDFT formulation. Absorption frequencies, singlet-triplet energy gaps and spin-orbit coupling (SOC) constants values were computed for all the investigated compounds. Results show how the sulfur- selenium- and iodine-substituted compounds possess improved properties that make them suitable for application in photodynamic therapy (PDT).

Photophysical Properties of Nitrated and Halogenated Phosphorus Tritolylcorrole Complexes: Insights from Theory.

The photophysical properties of a series of nitrated and halogenated phosphorus tritolylcorrole complexes were studied in dichloromethane solvent by using the density functional theory. Particular emphasis was given to the absorption spectra, the energy gap between the excited singlet and triplet states, and the magnitude of the spin-orbit couplings for a series of possible intersystem crossing channels between those excited states. The proposed study provides a better description of the photophysical properties of these systems while giving insights into their possible use as photosensitizers in photodynamic therapy.

Synergistic Effects in PtII -Porphyrinoid Dyes as Candidates for a Dual-Action Anticancer Therapy: A Theoretical Exploration.

The combination of a photosensitizer (PS) with a cisplatin-like unit represents a challenging strategy to increase the effectiveness of photodynamic therapy and to afford a dual-action anticancer treatment. Recently, new tetra-PtII -porphyrin conjugates have been proposed as promising multitarget agents. To reveal the effect of the PtII center on the chemical and physical properties of the PS and to explore the effect of the PS on the activation mechanism of PtII ligand before reaching its biological target, we carried out a first-principle investigation on these tetra-PtII -porphyrin conjugates. To propose a further advance in this novel field and to gain useful insights for the design of new, more efficient PtII -PS conjugates, we introduced structural modifications into the porphyrin dye, which involved the synthesis of the tetra-PtII -chlorin and tetra-PtII -bacteriochlorin derivatives. Results showed that the designed dyes better met the criteria to be successful in a dual-action therapy, as they displayed improved optical properties and reduced the hydrolysis rate of the PtII moiety, the latter being a desirable feature to avoid many side reactions of the conjugate during their transport to the biological target.

Theoretical Exploration of Type I/Type II Dual Photoreactivity of Promising Ru(II) Dyads for PDT Approach.

Ru(II) dyads are a class of bioactive molecules of interest as anticancer agents obtained incorporating an organic chromophore in the light-absorbing metallic scaffold. A careful DFT and TDDFT investigation of the photophysical properties of a series of Ru(II)-polypiridyl dyads containing polythiophene chains of different lengths bound to a coordinating imidazo[4,5-f][1,10]phenanthroline ligand is herein reported. The modulation of the crucial chemical and physical properties of the photosensitizer with increasing number of thiophene units has been accurately described by investigating the UV-vis spectra and type I and type II photoreactions, also including spin-orbit coupling values (SOC). Results show that the low-lying 3IL states afforded as the number of thiophene ligands increases (n = 3, 4) are energetically high enough to ensure singlet oxygen production and can be also involved in electron transfer reaction, showing a dual type I/type II photeoreactivity.

EH3 (E = N, P, As) and H2 activation with N-heterocyclic silylene and germylene homologues.

DFT calculations have been used to probe the mechanism of the addition reaction of group 15 hydrides EH3 (E = N, P, As) and H2 to a N-heterocyclic silylene and its germylene homologue. Nitrogen lone pair donation into the vacant p-orbital of Si and Ge is the first step of ammonia activation, whereas silylene and germylene behave as nucleophiles toward dihydrogen, phosphane, and arsane. Formation of 1,4-addition products is kinetically favoured in all cases. In excess ammonia, the assistance of a second molecule drastically lowers the 1,1-addition energy barriers, enabling formation of 1,1-addition products. The participation of a second molecule in the P-H bond activation of phosphane also lowers the 1,1-addition energy barriers, but not enough to cause inversion.