Study of the microscopic mechanism of stepwise charge injection in co-sensitive DSSCs in the framework of a D-π-A dye and chlorophyll.

The newly synthesized dye molecules TY6 and CXC22 were selected to explain the influence of anthracene and acetylene groups on the power conversion efficiency (PCE) of the molecules at the microscopic level. Theoretical simulation was carried out to understand the properties of the two molecules, including frontier molecular orbitals, absorption spectra, light absorption efficiency, intramolecular charge transfer (ICT), dye regeneration, I-V prediction, etc. The results suggest that for CXC22, adding an anthracene and acetylene group in the conjugate bridge greatly enhances the molecule's absorption wavelength and molar extinction coefficient; CXC22 also has significant advantages in the intramolecular charge transfer and comparatively better dye regeneration and electron injection. These parameters cause CXC22 to have a higher PCE. Subsequently, CXC22 and the chlorophyll molecule (CHL7) were selected for co-sensitization to regulate performance. The stable structure in the co-sensitization configuration was screened, and the absorption spectrum characteristics and charge transfer mechanisms were revealed for the co-sensitization system. The designed evaluation model predicted that the PCE of CO1 (the cosensitive system of CXC22 and TY6 in H-H configuration is referred to as CO1) could reach 16.78%. This work provides an idea for developing an efficient dye-sensitized solar cell system.

Photovoltaic performance and power conversion efficiency prediction of double fence porphyrins.

To explore high efficiency dye-sensitized solar cells (DSSCs), two experimentally derived (single fence and double fence porphyrins) and two theoretically designed zinc porphyrin molecules with D-D-π-A-A configurations were studied. Density functional theory and time-dependent density functional theory were employed to simulate these two experimental dyes and dye@TiO2 systems to understand why the double fence porphyrin molecule exhibits better photovoltaic performance than the single fence porphyrin molecule. For the short-circuit current (JSC), the various parameters that affected the experimental magnitude of JSC were analyzed from different aspects of absorption, charge transfer and chemical parameters as well as an electron injection process. The almost equal open-circuit voltages (VOC) in the experiment were predicted by theoretical VOC calculations. Our model predicted power conversion efficiencies (PCEs) of 1.993% and 10.866% for the single and double fence molecules, respectively, which are in accordance with the experimental values of 3.48% and 10.69%, respectively. In addition, one designed two new molecules based on the double fence porphyrin molecule with a 2-methyl-2H-benzo[d][1,2,3]triazole (BTA) unit bearing one fluorine and two fluorine atoms as the guest acceptor, respectively. Compared to the original molecules, the engineered molecules significantly improved the photovoltaic parameters, JSC and VOC, thereby causing excellent PCEs. The most outstanding designed molecule reached a PCE of 12.155%, and is considered a candidate dye for high-efficiency DSSC. This study provides insights into the photoelectric properties of single and double fence porphyrins. It also demonstrated that the strong electron-withdrawing ability of fluorine atoms would enhance the photovoltaic performance and provide a guideline for the further design of double fence porphyrins.

Effect of Polymerization on the Charge-Transfer Mechanism in the One (Two)-Photon Absorption Process of D-A-Type Triphenylamine Derivatives.

To investigate the effect of polymerization (n = 1, 2, 3, and 4) on the charge-transfer (CT) mechanisms in the one (two)-photon absorption (OPA and TPA) process of D-A-type triphenylamine derivatives, charge density difference is used to graphically represent the CT characteristics. A transition density matrix is utilized to reveal the direction of CT on different groups quantitatively. With the n increasing, electrons are mainly transferred between the groups in the middle position of the molecular chain during OPA and TPA processes. Simulated results show that the energy gap and excitation energy have a good linear relationship with the reciprocal of the polymerization degree. Importantly, the polymerization effect can effectively increase the electronic transmission capability, TPA performance, and second hyperpolarizability. Besides, the simplified sum over state model reveals the variation factor of the TPA cross-section and the second static hyperpolarizability. The McRae formula and Bakhshiev formula are used to estimate the difference of dipole moments, which is an important parameter of the second hyperpolarizability. The comprehensive analysis of the nonlinear optical (NLO) parameters of triphenylamine derivatives can provide some significant guidance for molecular design and improve the NLO performance of D-A molecular materials. Also, the thermodynamic parameters can provide some theoretical supports for solving practical problems.

Effect of graphene between photoanode and sensitizer on the intramolecular and intermolecular electron transfer process.

The main goal of this work is to investigate the effects of a graphene layer between the photosensitive layer and semiconductor substrates on the electron transport performance of dye-sensitized solar cells from the perspective of intramolecular arrangement and interfaces. The benzothiadiazole sensitizer YKP-88 is used as the photosensitive layer and the influence of the graphene layer on the short-circuit current density (Jsc) and open-circuit voltage (Voc) is also discussed by exploring the frontier molecular orbitals, intramolecular charge transfer, weak interaction, interfacial electron dynamic propagations and other microscopic parameters after the anchoring of the graphene layer. The results demonstrate that the graphene layer can accelerate the electron injection of dye molecules into the semiconductor substrate, which not only has a qualitative reduction in injection time, but also has a qualitative change in the increase of the injection amount. In addition, it is also found that the graphene layer increases the stereoscopic effect, the absorption of long wavelength (>700 nm) photon flu and the amount of electron injection into the photoanode, which benefits the intramolecular charge transfer and increases the Jsc and Voc of solar cells. The combination of intermolecular and interfacial perspectives indicates that the appropriate configuration of graphene layers can effectively improve the photoelectric conversion efficiency of dye-sensitized solar cells.

Characterization and Evaluation of the Solubility and Oral Bioavailability of Rutin-Ethanolate Solvate.

Rutin has many biological activities, but poor solubility and absorption limit its oral application. This study aimed to investigate the characterization of metastable rutin-ethanolate and its solubility and oral bioavailability. In this research, a soluble rutin/CH3CH2OH solvate (Form Π) was prepared by solvent crystallization. High-performance liquid chromatography, gas chromatograph, and 1H-NMR showed that Form Π was formed by rutin and ethanol in a molar ratio of 1:1. The changes of Fourier transform infrared spectroscopy and 1H-NMR spectrum and the density functional theory (DFT) calculation predicted hydrogen bond formation between 4'-O of rutin and -OH of ethanol. The results of morphology, solid state CP/MAS 13C-NMR, X-ray diffraction, and differential scanning calorimetry (DSC) revealed that Form Π is a novel polymorph that differs from Form Ι (rutin trihydrate). Form Π can be stored for a long time under sealed and dry conditions at 40°C but would gradually transform into Form Ι under humid conditions. Although Form Π is a new metastable polymorph relative to Form Ι, Form Π has better solubility and faster dissolution rate. Moreover, the bioavailability of Form Π was 2.04 times higher than that of Form Ι. This outcome implied that Form Π would be a prospective raw material of oral preparation.

Second-Order Nonlinear Optical Switch Manipulation of Photosensitive Layer by an External Electric Field Coupled with Graphene Quantum Dots.

The main purpose of this work is to explore the effect of graphene quantum dots (GR) filling the photosensitive layer. The multibranched dye JH-1 as the photoactive layer material was used to analyze the non-negligible role of graphene quantum dots from the perspectives of optimized structure, electrochemical parameters, optical properties, nonlinear optical (NLO) switch, and external electric field. The results demonstrated that the graphene quantum dots not only improve the optical properties of solar cells but also control the electron transfer in the photosensitive layer molecules under the manipulation of a specific external electric field. When the external electric field intensity is below 20 × 10-4 au, the excess electron orbital does not change. When the external electric field reaches 25 × 10-4 au, the excess electron orbital on the graphene quantum dots evolves. This discovery allows the electron transfer from the photosensitive layer, which should be controlled by the NLO switch. In addition, the optical properties of sensitizers showed regular evolution in the external electric field, which provides an effective way to improve the performance. Comprehensive analysis indicated that the doping of graphene quantum dots with the photosensitive layer can be used as a new way to improve the photoelectric conversion efficiency of solar cells.

Tuning the Electron-Transport and Electron-Accepting Abilities of Dyes through Introduction of Different π-Conjugated Bridges and Acceptors for Dye-Sensitized Solar Cells.

A series of dyes, containing thiophene and thieno[3,2-b]thiophene as π-conjugated bridging units and six kinds of groups as electron acceptors, were designed for dye-sensitized solar cells (DSSCs). The ground- and excited-state properties of the designed dyes were investigated by using density functional theory (DFT) and time-dependent DFT, respectively. Moreover, the parameters affecting the short-circuit current density and open-circuit voltage were calculated to predict the photoelectrical performance of each dye. In addition, the charge difference density was presented through a three-dimensional (3D) real-space analysis method to investigate the electron-injection mechanism in the complexes. Our results show that the longer conjugated bridge would inhibit the intramolecular charge transfer, thereby affecting the photoelectrical properties of DSSCs. Similarly, owing to the lowest chemical hardness, largest electron-accepting ability, dipole moment (µnormal ) and the change in the energy of the TiO2 conduction band (ΔECB ), the dye with a (E)-3-(4-(benzo[c][1,2,5]thiadiazol-4-yl)phenyl)-2-cyanoacrylic acid (TCA) acceptor group would exhibit the most significant photoelectrical properties among the designed dyes.

Vibronic quantized tunneling controlled photoinduced electron transfer in an organic solar cell subjected to an external electric field.

In this work, vibration-resolved photoinduced electron transfer of an organic conjugated DA system subjected to an external electric field was theoretically investigated. The ground and excited state vibrational relaxation energies were quantitatively characterized. The effective high frequency, ωeff, could be estimated from the variation in energy of the excited-state equilibrium geometries of acceptor and donor sites as well as the analysis of the vibrational modes upon electron transfer. For a PCDTBT:PC70BM blend in an external electric field, the vibronic modes affected the charge separation process differently from the charge recombination process. The simulated results indicated that the vibrational quantum tunneling effect facilitated the charge recombination process to a large extent. Thus, for electron transfer reactions, considering the vibrational excitation influence and perturbed nucleus-electron interactions is essential. These results provide a feasible way to enhance the efficiency in yielding the electron transfer process products.

Photoinduced Electron Transfer in Organic Solar Cells.

Electron transfer (ET) is the key process in light-driven charge separation reactions in organic solar cells. The current review summarizes the progress in theoretical modelling of ET in these materials. First we give an account of ET, with a description originating from Marcus theory. We systematically go through all the relevant parameters and show how they depend on different material properties, and discuss the consequences such dependencies have for the performance of the devices. Finally, we present a set of visualization methods which have proven to be very useful in analyzing the elementary processes in absorption and charge separation events. Such visualization tools help us to understand the properties of the photochemical and photobiological systems in solar cells.

Effect of electronic acceptor segments on photophysical properties of low-band-gap ambipolar polymers.

Stimulated by a recent experimental report, charge transfer and photophysical properties of donor-acceptor ambipolar polymer were studied with the quantum chemistry calculation and the developed 3D charge difference density method. The effects of electronic acceptor strength on the structure, energy levels, electron density distribution, ionization potentials, and electron affinities were also obtained to estimate the transporting ability of hole and electron. With the developed 3D charge difference density, one visualizes the charge transfer process, distinguishes the role of molecular units, and finds the relationship between the role of DPP and excitation energy for the three polymers during photo-excitation.

Nonlinear optical properties and optimization strategies of D-π-A type phenylamine derivatives in the near-infrared region.

Modifying simple molecular structures to significantly improve nonlinear optical (NLO) performance is a primary prerequisite for scientific research. Based on the four phenylamine derivatives reported in previous studies, we designed four organic nonlinear molecules by changing the acceptor group and π-linker. (Time-dependent) density functional theory (DFT/TD-DFT) was performed on molecular geometry optimization, the contribution of π electrons to the bond order, linear and two-photon absorption (TPA) spectra, the intra-molecular charge transfer matrix (CTM), and NLO coefficients. These aspects were considered to analyze in detail how the structural modification of acceptors and π-linkers affects NLO characteristics. The three modification methods were: adding a carbonyl group at the junction of the π-linker and the acceptor group, adding a carbonyl group and a nitrogen atom to the acceptor group, and replacing the quinolinone with a pyrenyl group as the π-linker. The latter two methods can significantly reduce the excitation energy and enhance the intensity of intra-molecular charge transfer during the two-photon transition. The maximum TPA cross-sections and wavelengths of the designed molecules are DPPM (84722.6 GM, 815.7 nm) and DDPM (21600.6 GM, 781.3 nm). These two molecules have large TPA cross-sections in the near-infrared region, which renders them as possible NLO materials with broad application prospects.

Unveiling the influence of atomic electronegativity on the double ESIPT processes of uralenol: A theoretical study.

In this work, the effects of atomic electronegativity (O, S, and Se atoms) on the competitive double excited-state intramolecular proton transfer (ESIPT) reactions and photophysical characteristics of uralenol (URA) were systematically explored by using the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The calculated hydrogen bond parameters, infrared (IR) vibrational spectra, reduced density gradient (RDG) scatter plots, interaction region indicator (IRI) isosurface and topology parameters have confirmed the six-membered intramolecular hydrogen bond (IHB) O4H5…O3 is the stronger one in all the three studied compounds. Subsequently, frontier molecular orbitals (FMOs) and natural bond orbital (NBO) population analysis essentially uncover that the electron redistribution has induced the ESIPT process. Besides, the constructed potential energy curves (PECs) have indicated that the ESIPT process prefers to occur along the O4H5…O3 rather than the O1H2…O3 and the proton-transfer energy barrier is gradually decreased with the weakening of atomic electronegativity from URA to URA-S and URA-Se. In a conclusion, the attenuating of atomic electronegativity has enhanced the IHBs of URA and thereby promoting the ESIPT reaction, which is helpful for further developing novel fluorophores based on ESIPT behavior in the future.

Tactfully unveiling the effect of solvent polarity on the ESIPT mechanism and photophysical property of the 3-hydroxylflavone derivative.

In this contribution, the solvent effects on the excited-state intramolecular proton transfer (ESIPT) and photophysical properties of 2-(4-(diphenylamine)phenyl)-3-hydroxy-4H-chromen-4-one (3HF-OH, Dyes Pigm. 2021, 184, 108865) in the dimethylsulfoxide (DMSO), acetonitrile (ACN), dichloromethane (DCM) and cyclohexane (CYH) phases have been comprehensively explored by using the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The obtained bond lengths, bond angles and infrared (IR) vibration analysis related to the intramolecular hydrogen bond (IHB) reveal that the IHB intensity of 3HF-OH is weakened as the solvent polarity increased. Besides, the ESIPT process changes from the endothermic to the exothermic with the enlargement of solvent polarity, and the reaction barrier increases gradually. It is worth noting that the molecular configuration torsion of 3HF-OH is gradually intensified with the decline of solvent polarity, which aggravates the twisted intramolecular charge transfer (TICT) state and thereby partially attenuates the short-wavelength fluorescence of 3HF-OH in the CYH solvent. In addition to these, the structural torsion has restrained the occurrence of the ESIPT behavior by means of elevating the energy barrier. This theoretical research would provide valuable guidance for regulating and controlling the photophysical behavior of compounds via the strategy of changing solvent polarity.

Enhancement of one- and two-photon absorption and visualization of intramolecular charge transfer of pyrenyl-contained derivatives.

To further improve the pyrenyl-contained derivatives two-photon absorption (TPA) and third-order nonlinear optical (NLO) properties, three steps of optimization are employed based on experimental molecule PCVS-B: heteroatomic substitution, exchanging the position of double bonds and adding a branch. The contributions of π electrons to localized orbital locators and Mayer bond orders (LOL-π and IABπ) show that the second step can enhance the chemical interaction between pyrenyl and the branched-chain. Two visual methods of charge density difference (CDD) and transition density matrix (TDM) are combined to intuitively analyze the intramolecular charge transfer (ICT) process of one (two) photon absorption; results show that both following two steps can increase the degree of ICT on the conjugated plane of the pyrenyl. The sum over state (SOS) model was used to find out the dominant two-photon transition process. The difference between the dipole moments obtained by the McRae equation is applied to the three-state model, revealing the inherent law of the second static hyperpolarizability.

Improving the antioxidant activity of natural antioxidant honokiol by introducing the amino group.

Exploring and synthesizing the compounds with stronger antioxidant activity have always been the goal of researchers. Herein, the substitution effects of the amino (NH2-) group with the excellent electron-donating ability in different positions on the antioxidant activity of Honokiol (Hon) were systematically explored by using the quantum chemistry calculation based on the density functional theory method. The three possible antioxidant mechanisms of Hon and its four NH2-substituted derivatives (Hon1-Hon4), containing the hydrogen atom transfer (HAT), single electron transfer followed by proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET), were explored in depth considering the gas and solvent phases. In addition, the frontier molecular orbital energies, natural bond orbital (NBO) charge population, and global descriptive parameters were used to study their antioxidant activity. The results indicate that compared with the original molecule Hon, the NH2 substituents would have the stronger antioxidant activity. Moreover, the radical scavenging process of Hon and its derivatives has a disposition to the HAT and SPLET mechanisms in the gas and solvent phases, respectively. Meaningfully, owing to the lowest bond dissociation enthalpy and proton affinity values, Hon4 would show the most prominent antioxidant activity by comparison with the other compounds. In conclusion, this work will provide the purposeful reference for designing and synthesizing the antioxidants with more outstanding performance.

Novel Triarylamine-Based Hole Transport Materials: Synthesis, Characterization and Computational Investigation.

Three novel triarylamine-based electron-rich chromophores were synthesized and fully characterized. Compounds 1 and 2 were designed with electron-rich triphenylamine skeleton bearing two and four decyloxy groups namely, 3,4-bis(decyloxy)-N,N-diphenylaniline and N-(3,4-bis(decyloxy)phenyl)-3,4-bis(decyloxy)-N-phenylaniline, respectively. The well-known electron-rich phenothiazine was introduced to diphenylamine moiety through a thiazole ring to form N,N-bis(3,4-bis(decyloxy)phenyl)-5-(10H-phenothiazin-2-yl)thiazol-2-amine (Compound 3). These three novel compounds were fully characterized and their UV-vis absorption indicated their transparency as a favorable property for hole transport materials (HTMs) suitable for perovskite solar cells. Cyclic voltammetry measurements revealed that the HOMO energy levels were in the range 5.00-5.16 eV for all compounds, indicating their suitability with the HOMO energy level of the perovskite photosensitizer. Density functional theory (DFT) and time-dependent DFT (TD-DFT) have been used to investigate the possibility of the synthesized compounds to be utilized as HTMs for perovskite solar cells (PSCs). The computational investigation revealed that the hole mobility of Compound 1 was 1.08 × 10-2 cm2 V-1 s-1, and the substitution with two additional dialkoxy groups on the second phenyl ring as represented by Compound 2 significantly boosted the hole mobility to reach the value 4.21 × 10-2 cm2 V-1 s-1. On the other hand, Compound 3, in which the third phenyl group was replaced by a thiazole-based phenothiazine, the value of hole mobility decreased to reach 5.93 × 10-5 cm2 V-1 s-1. The overall results indicate that these three novel compounds could be promising HTMs for perovskite solar cells.

Ascertaining p,p'-dimercaptoazobenzene produced from p-aminothiophenol by selective catalytic coupling reaction on silver nanoparticles.

Combining experiment and theory, evidence from surface-enhanced Raman scattering (SERS) were obtained for p,p'-dimercaptoazobenzene (DMAB) produced from p-aminothiophenol (PATP) by selective catalytic coupling reaction on silver nanoparticles. The time-dependent SERS spectra of PATP are consistent with the calculated SERS spectra of DMAB, which is the direct evidence for the production of DMAB from PATP by selective catalytic coupling reaction on silver nanoparticles. The so-called "b(2) modes" of PATP is the -N=N- related vibrational modes of DMAB. The silver nanoparticles could be assembled together to form different size of aggregates with different concentration of PATP solution. When the concentration of Ag nanoparticle (the radius 40 nm) in colloid is 35 pM, the time-dependent SERS of DMAB reveals that the better experimental conditions for observing SERS signals of DMAB are (1) concentration of PATP is around 5 x 10(-6) M in which condition the aggregates consist with about 3-5 silver nanoparticles, which are not too big and suitable for SERS measurement, and (2) the Raman signal will be strongest at the time delay about 27 min for this concentration. By analyzing the symmetry of strong enhanced vibrational modes, it is derived that all of six strong vibrational modes are mostly enhanced by surface plasmons (electromagnetic field). The SERS enhancement calculated with finite-difference time-domain method is on the order of |M|(4) = 9.0 x 10(8) in junctions of AgNPs at 632.8 nm, where |M| = E(loc)/E(in), and E(loc) and E(in) are local and incident electric fields, respectively. The total chemical enhancements, including static chemical and resonant enhancements, are on the order of 10(3).

Electronic structure and optical properties of dianionic and dicationic pi-dimers.

The absorption spectra of dianionic tetrocyanoethylene and dicationic tetrathiafulvalene dimers have been studied theoretically with the time-dependent density functional theory and the recently proposed Coulomb-attenuated model. The nature of the excited states was further explored by means of the two-dimensional (2D) site (transition density matrix) and three-dimensional (3D) cube (transition density and charge difference density) representations. By use of the 3D transition density and charge difference density, we visualized the orientation of transition dipole moment and also explained charge-transfer characteristics occurring in the dianionic/dicationic pi-dimers system. It is found that for the dianionic/dicationic pi-dimers system there exist two kinds of charge-transfer patterns for the mainly excited states, the intermolecular charge transfer and the mixture of intramolecular charge transfer coupled with intermolecular charge transfer. Meanwhile, the coupling effect of excitation and the oscillation of electron-hole pairs between the monomers have been revealed with 2D site representation of transition density matrix, which also indicates the electron-hole coherence upon photon excitation.

Theoretical Investigation on Photophysical Properties of Triphenylamine and Coumarin Dyes.

Organic molecules with donor and acceptor configures are widely used in optoelectronic materials. Triphenylamine dyes (TPCTh and TPCRh) are investigated via density functional theory (DFT) and time-dependent DFT. Some microscopic parameters related to light absorption and photoelectric formation are calculated to interpret the experimental performance in dye-sensitized solar cells (DSSCS). Considering that coumarin derivatives (Dye 10 and Dye 11) have good donor and acceptor structures, they also have a COOH group used as an anchoring group to connect with semiconductors. Thus, the two dyes' photophysical and photoelectric properties are analyzed to estimate the performance and application in DSSCs.

Screening of functional monomers and solvents for the molecular imprinting of paclitaxel separation: a theoretical study.

The interactions between the template molecule paclitaxel (PTX) and seven functional monomers containing methacrylic acid (MA), acrolein (AC), 4-vinylbenzoic acid (4VA), acrylonitrile (AN), 2-vinylpyridine (2VP), 2,6-bisacrylamide pyridine (BAP) and methyl methacrylate (MM) were systematically investigated adopting the density functional theory (DFT) method. Moreover, the different binding sites on PTX and solvents embracing chloroform, acetone, ethanol, methanol, and acetonitrile were considered. The calculated solvent energies (ΔEsolvent) and template-monomer binding energies (ΔEb) suggest that the chloroform is the most suitable solvent for the molecular imprinting reaction of PTX among the studied five solvents. Furthermore, from the obtained ΔEb, we can find that the monomer 4VA combining with PTX in the form of the specific intermolecular hydrogen bonds would present the most stable structure among the investigated monomers. These results can provide valuable theoretical guidance for the efficient extraction of PTX by the molecular imprinting technique in experiments. Graphical abstracts.