Absorption spectra of p-nitroaniline derivatives: charge transfer effects and the role of substituents.

CONTEXT: Push-pull compounds are model systems and have numerous applications. By changing their substituents, properties are modified and new molecules for different applications can be designed. The work investigates the gas-phase electronic absorption spectra of 15 derivatives of push-pull para-nitroaniline (pNA). This molecule has applications in pharmaceuticals, azo dyes, corrosion inhibitors, and optoelectronics. Both electron-donor and electron-withdrawing groups were investigated. Employing machine learning-derived Hammett's constants σm, σm0, σR, and σI, correlations between substituents and electronic properties were obtained. Overall, the σm0 constants presented the best correlation with HOMO and LUMO energies, whereas the σR constants best agreed with the transition energy of the first band and HOMO-LUMO energy gap. Electron-donors, which have lower σR values, redshift the absorption spectrum and reduce the HOMO-LUMO energy gap. Conversely, electron-withdrawing groups (higher σR's) blueshift the spectrum and increase the energy gap. The second band maximum energies, studied here for the first time, showed no correlation with σ but tended to increase with σ. A comprehensive charge transfer (CT) analysis of the main transition of all systems was also carried out. We found that donors (lower σ's) slightly enhance the CT character of the unsubstituted pNA, whereas acceptors (higher σ's) decrease it, leading to increased local excitations within the aromatic ring. The overall CT variation is not large, except for pNA-SO2H, which considerably decreases the total CT value. We found that the strong electron donors pNA-OH, pNA-OCH3, and pNA-NH2, which have the smallest HOMO-LUMO energy gaps and lowest σ's, have potential for optoelectronic applications. The results show that none of the studied molecules is fluorescent in the gas phase. However, pNA-NH2 and pNA-COOH in cyclohexane and water reveal fluorescence upon solvation. METHODS: We investigated theoretically employing the second-order algebraic diagrammatic construction (ADC(2)) ab initio wave function and time-dependent density functional theory (TDDFT) the gas-phase electronic absorption spectra of 15 derivatives of p-nitroaniline (pNA). The investigated substituents include both electron-donor (C6H5, CCH, CH3, NH2, OCH3, and OH,) and electron-withdrawing (Br, CCl3, CF3, Cl, CN, COOH, F, NO2, and SO2H) substituents.

Electrochemical Doping Effect on the Conductivity of Melanin-Inspired Materials.

Eumelanin is a natural pigment that can be particularly valuable for sustainable bioelectronic devices due to its inherent biocompatibility and hydration-dependent conductivity. However, the low conductivity of eumelanin limits its technological development. In this research, electrochemical doping was proposed as an alternative route to increase the electronic conductivity of synthetic eumelanin derivatives. Thin films of sulfonated eumelanin were deposited on platinum interdigitated electrodes and electrochemically treated by using cyclic voltammetry and chronoamperometry treatments. X-ray photoelectron spectroscopy analysis confirmed ion doping in sulfonated melanin. Current-voltage, current-time, and electrochemical impedance measurements were used to investigate the effect of different aqueous electrolytes (including KCl and LiClO4) treatments on the charge transport of sulfonated eumelanin. We show that the conductivity depends on the type and size of the anion used and can reach 10-3 S·cm-1. Additionally, depending on the electrolyte, there is a change in charge transport from mixed ionic/electronic to a predominantly electronic-only conduction. Our results show that the chemical nature of the ion plays an important role in the electrochemical doping and, consequently, in the charge transport of eumelanin. These insights serve as inspiration to explore the use of alternative electrolytes with different compositions further and develop eumelanin-based devices with tunable conductivities.

Insights into the Effect of Charges on Hydrogen Bonds.

Previous computational and experimental studies showed that charges located at the surroundings of hydrogen bonds can exert two opposite effects on them: rupture or strengthening of the hydrogen bond. This work aims to generalize the effect of charges in different hydrogen-bonded systems and to propose a coherent explanation of this effect. For these purposes, 19 systems with intra- and intermolecular hydrogen bonds were studied computationally with DFT. The FT-IR spectra of the systems were simulated, and two energy components of the hydrogen bond were studied separately to determine their variation upon the presence of a charge: charge transfer and molecular overlap. It was determined that either the breaking or strengthening of the hydrogen bond can be favored one over the other, for instance, depending on the heteroatom involved in the hydrogen bond. In addition, it is showed that the strengthening of the hydrogen bond by the presence of a charge is directly related to the decrease in charge transfer between the monomers, which is explained by an increase in molecular overlapping, suggesting a more covalent character of the interaction. The understanding of how hydrogen bonds are affected by charges is important, as it is a key towards a strategy to manipulate hydrogen bonds at convenience.

Photophysical Analysis of Aggregation-Induced Emission (AIE) Luminogens Based on Triphenylamine and Thiophene: Insights into Emission Behavior in Solution and PMMA Films.

Aggregation-Induced Emission (AIE) luminogens have garnered significant interest due to their distinctive applications in different applications. Among the diverse molecular architectures, those based on triphenylamine and thiophene hold prominence. However, a comprehensive understanding of the deactivation mechanism both in solution and films remains lacking. In this study, we synthesized and characterized spectroscopically two AIE luminogens: 5-(4-(bis(4-methoxyphenyl)amino)phenyl)thiophene-2-carbaldehyde (TTY) and 5'-(4-(bis(4-methoxyphenyl)amino)phenyl)-[2,2'-bithiophene]-5-carbaldehyde (TTO). Photophysical and theoretical analyses were conducted in both solution and PMMA films to understand the deactivation mechanism of TTY and TTO. In diluted solutions, the emission behavior of TTY and TTO is influenced by the solvent, and the deactivation of the excited state can occur via locally excited (LE) or twisted intramolecular charge transfer (TICT) state. In PMMA films, rotational and translational movements are constrained, necessitating emission solely from the LE state. Nevertheless, in the PMMA film, excimers-like structures form, resulting in the emergence of a longer wavelength band and a reduction in emission intensity. The zenith of emission intensity occurs when molecules are dispersed at higher concentrations within PMMA, effectively diminishing the likelihood of excimer-like formations. Luminescent Solar Concentrators (LSC) were fabricated to validate these findings, and the optical efficiency was studied at varying concentrations of luminogen and PMMA.

3-Halochromones Through Oxidative α-Halogenation of Enaminones and its Photophysical Investigation: Another Case of Photo-induced Partially Aromatised Intramolecular Charge Transfer?

A versatile synthesis strategy for fluorescent 3-halo-4H-chromen-4-one derivatives is reported. The method involves the oxidative α-halogenation of enaminones performed by an efficient and sustainable oxidation system. The use of Oxone® in combination with KCl, KBr, or KI enables the preparation of 3-chloro-, 3-bromo-, or 3-iodo-4H-chromen-4-one in good to excellent yields, with great functional group tolerance where the protocol is amenable to gram-scale synthesis. The analysis of the photophysical properties of the presented 4H-chromen-4-one showed absorption in the UV region and fluorescence emission in the violet-to-cyan region with a relatively large Stokes shift. In solution, all compounds present a dual fluorescence emission, regardless of the solvent, assigned to a partially aromatised intramolecular charge transfer mechanism, considering the presence of a pseudo-aromatic ring in the chromone scaffold and the absence of the influence of substituent electronic features in optical behaviour.

A comprehensive analysis of charge transfer effects on donor-pyrene (bridge)-acceptor systems using different substituents.

The alternant polycyclic aromatic hydrocarbon pyrene has photophysical properties that can be tuned with different donor and acceptor substituents. Recently, a D (donor)-Pyrene (bridge)-A (acceptor) system, DPA, with the electron donor N,N-dimethylaniline (DMA), and the electron acceptor trifluoromethylphenyl (TFM), was investigated by means of time-resolved spectroscopic measurements (J. Phys. Chem. Lett. 2021, 12, 2226-2231). DPA shows great promise for potential applications in organic electronic devices. In this work, we used the ab initio second-order algebraic diagrammatic construction method ADC(2) to investigate the excited-state properties of a series of analogous DPA systems, including the originally synthesized DPAs. The additionally investigated substituents were amino, fluorine, and methoxy as donors and nitrile and nitro groups as acceptors. The focus of this work was on characterizing the lowest excited singlet states regarding charge transfer (CT) and local excitation (LE) characters. For the DMA-pyrene-TFM system, the ADC(2) calculations show two initial electronic states relevant for interpreting the photodynamics. The bright S1 state is locally excited within the pyrene moiety, and an S2 state is localized ~0.5 eV above S1 and characterized as a donor to pyrene CT state. HOMO and LUMO energies were employed to assess the efficiency of the DPA compounds for organic photovoltaics (OPVs). HOMO-LUMO and optical gaps were used to estimate power conversion and light-harvesting efficiencies for practical applications in organic solar cells. Considering the systems using smaller D/A substituents, compounds with the strong acceptor NO2 substituent group show enhanced CT and promising properties for use in OPVs. Some of the other compounds with small substituents are also found to be competitive in this regard.

Studies on charge transfer of enalapril maleate: from solid-state to molecular dynamics.

INTRODUCTION: Enalapril maleate is an antihypertensive ethyl ester pro-drug with two crystalline forms. A network of hydrogen bonds in both polymorphs plays an important role on solid-state stability, charge transfer process and degradation reactions (when exposed to high humidity, temperature and/or pH changes). COMPUTATIONAL PROCEDURES: Supramolecular arrangement was proposed by Hirshfeld surface using the CrystalExplorer17 software and quantum theory of atoms in molecules. The electronic structure properties were calculated using the functional hybrid M06-2X with 6-311++G** base function employing diffuse and polarization functions to improve the description of hydrogen atoms on intermolecular interactions. Also, the H+ charge transfer between enalapril and maleate molecules was performed using Car-Parrinello molecular dynamics with the Verlet algorithm. In both simulations, the temperature of the ionic system was maintained around 300 K using the Nosé-Hoover thermostat and the electronic system evolved without the use of the thermostat. RESULTS: This work evaluates the effect of maleate on the structural stability of enalapril maleate solid state. The electronic structural analysis points out a partially covalent character for N1-H∙∙∙O7 interaction; and the molecular dynamic showed a decentralized hydrogen on maleate driving a decomposition by charge transfer process while a centered hydrogen driving the stabilization. The charge transfer process and the mobility of the proton (H+) between enalapril and maleate molecules was demonstrated using supramolecular modeling analyses and molecular dynamics calculations.

Graphene Mediates Charge Transfer between Lead Chromate and a Cobalt Cubane Cocatalyst for Photocatalytic Water Oxidation.

The interfacial barrier of charge transfer from semiconductors to cocatalysts means that the photogenerated charges cannot be fully utilized, especially for the challenging water oxidation reaction. Using cobalt cubane molecules (Co4 O4 ) as water oxidation cocatalysts, we rationally assembled partially oxidized graphene (pGO), acting as a charge-transfer mediator, on the hole-accumulating {-101} facets of lead chromate (PbCrO4 ) crystal. The assembled pGO enables preferable immobilization of Co4 O4 molecules on the {-101} facets of the PbCrO4 crystal, which is favorable for the photogenerated holes transferring from PbCrO4 to Co4 O4 molecules. The surface charge-transfer efficiency of PbCrO4 was boosted by selective assembly of pGO between PbCrO4 and Co4 O4 molecules. An apparent quantum efficiency for photocatalytic water oxidation on the Co4 O4 /pGO/PbCrO4 photocatalyst exceeded 10 % at 500 nm. This strategy of rationally assembling charge-transfer mediator provides a feasible method for acceleration of charge transfer and utilization in semiconductor photocatalysis.

Improved charge-transfer resonance in graphene oxide/ZrO2 substrates for plasmonic-free SERS determination of methyl parathion.

This work reports a sensitive SERS substrate based on graphene oxide (GO) and quantum-sized ZrO2 nanoparticles (GO/ZrO2) for label-free determination of the organophosphate pesticide methyl parathion (MP). The enhanced light-matter interactions and the consequent SERS effect in these substrates resulted from the effective charge transfer (CT) mechanism attributed to synergistic contributions of three main factors: i) the strong molecular adherence of the MP molecules and the ZrO2 surface which allows the first layer-effect, ii) the relatively abundant surface defects in low dimensional ZrO2 semiconductor NPs, which act as intermediate electronic states that reduce the large bandgap barrier, and iii) the hindered charge recombination derived from the transference of the photoinduced holes to the GO layer. This mechanism allowed an enhancement factor of 8.78 × 104 for GO/ZrO2-based substrates, which is more than 5-fold higher than the enhancement observed for platforms without GO. A detection limit of 0.12 µM was achieved with an outstanding repeatability (variation ≤4.5%) and a linear range up to 10 µM, which is sensitive enough to determine the maximal MP concentration permissible in drinking water according to international regulations. Furthermore, recovery rates between 97.4 and 102.1% were determined in irrigation water runoffs, strawberry and black tea extracts, demonstrating the reliability of the hybrid GO/ZrO2 substrate for the organophosphate pesticides quantification in samples related to agri-food sectors and environmental monitoring.

Carbon dots decorated magnetite nanocomposite obtained using yerba mate useful for remediation of textile wastewater through a photo-Fenton treatment: Ilex paraguariensis as a platform of environmental interest-part 2.

Two carbon dots (CD) with diameters of 4.9 ± 1.5 and 4.1 ± 1.2 nm were successfully synthesized through an acid ablation route with HNO3 or H2SO4, respectively, using Ilex paraguariensis as raw material. The CD were used to produce magnetite-containing nanocomposites through two different routes: hydrothermal and in situ. A thorough characterization of the particles by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), dynamic light scattering (DLS), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) indicates that all nanomaterials have spherical-like morphology with a core-shell structure. The composition of this structure depends on the route used: with the hydrothermal route, the shell is composed of the CD, but with the in situ process, the CD act as nucleation centers, and so the iron oxide domains are in the shell. Regarding the photocatalytic mechanism for the degradation of methyl orange, the interaction between the CD and the magnetite plays an important role in the photo-Fenton reaction at pH 6.2, in which ligand-to-metal charge transfer processes (LTMCT) allow Fe2+ regeneration. All materials (100 ppm) showed catalytic activity in the elimination of methyl orange (8.5 ppm), achieving discoloration of up to 98% under visible irradiation over 400 nm in 7 h. This opens very interesting possibilities for the use of agro-industrial residues for sustainable synthesis of catalytic nanomaterials, and the role of the interaction of iron-based catalysts with organic matter in heterogeneous Fenton-based processes.

Computational Quantification of the Zwitterionic/Quinoid Ratio of Phenolate Dyes for Their Solvatochromic Prediction.

Solvatochromic dyes are utilized in various chemical and biological media as chemical sensors. Unfortunately, there is no simple way to predict the type of solvatochromism based on the structure of the dye alone, which restricts their design and synthesis. The most important family of solvatochromic sensors, pyridinium phenolate dyes, has the strongest solvatochromism. Using a natural population analysis (NPA) of the natural bond orbitals (NBO) of the phenolate group in the frontier molecular orbitals, it is possible to calculate the relative polarity of the ground state and excited state and, thus to develop a model that can predict the three types of solvatochromism observed for this family: negative, positive, and inverted. This methodology has been applied to thirteen representative examples from the literature. Our results demonstrate that the difference in the electron density of the phenolate moiety in the frontier molecular orbitals is a simple and inexpensive theoretical indicator for calculating the relative polarity of the ground and excited states of a representative library of pyridinium phenolate sensors, and thus predicting their solvatochromism. Comparing the results with the bond length alternation (BLA) and bond order alternation (BOA) indices showed that the NPA/NBO method is a better way to predict solvatochromic behavior.

A Detailed Study of Electronic and Dynamic Properties of Noble Gas-Oxygen Molecule Adducts.

In this work, the binding features of adducts formed by a noble gas (Ng = He, Ne, Ar, Kr, Xe, and Rn) atom and the oxygen molecule (O2) in its ground Σg-3, in the past target of several experimental studies, have been characterized under different theoretical points of view to clarify fundamental aspects of the intermolecular bond. For the most stable configuration of all Ng-O2 systems, binding energy has been calculated at the theory's CCSD(T)/aug-cc-pVTZ level and compared with the experimental findings. Rovibrational energies, spectroscopic constants, and lifetime as a function of temperature were also evaluated by adopting properly formulated potential energy curves. The nature of the interaction involved was deeply investigated using charge displacement analysis, symmetry-adapted perturbation theory (SAPT), and natural bond orbital (NBO) methods. In all adducts, it was found that the charge transfer plays a minor role, although O2 is an open shell species exhibiting a positive electron affinity. Obtained results also indicate that the dispersion attraction contribution is the main responsible for the complex stability.

CO2 Adsorption over 3d Transition-Metal Nanoclusters Supported on Pyridinic N3-Doped Graphene: A DFT Investigation.

CO2 adsorption on bare 3d transition-metal nanoclusters and 3d transition-metal nanoclusters supported on pyridinic N3-doped graphene (PNG) was investigated by employing the density functional theory. First, the interaction of Co13 and Cu13 with PNG was analyzed by spin densities, interaction energies, charge transfers, and HUMO-LUMO gaps. According to the interaction energies, the Co13 nanocluster was adsorbed more efficiently than Cu13 on the PNG. The charge transfer indicated that the Co13 nanocluster donated more charges to the PNG nanoflake than the Cu13 nanocluster. The HUMO-LUMO gap calculations showed that the PNG improved the chemical reactivity of both Co13 and Cu13 nanoclusters. When the CO2 was adsorbed on the bare 3d transition-metal nanoclusters and 3d transition-metal nanoclusters supported on the PNG, it experienced a bond elongation and angle bending in both systems. In addition, the charge transfer from the nanoclusters to the CO2 molecule was observed. This study proved that Co13/PNG and Cu13/PNG composites are adequate candidates for CO2 adsorption and activation.

Photoinduced Intervalence Charge Transfers: Spectroscopic Tools to Study Fundamental Phenomena and Applications.

The exploitation of excited state chemistry for solar energy conversion or photocatalysis has been continuously increasing, and the needs of a transition to a sustainable human development indicate this trend will continue. In this scenario, the study of mixed valence systems in the excited state offers a unique opportunity to explore excited state electron transfer reactivity, and, in a broader sense, excited state chemistry. This Concept article analyzes recent contributions in the field of photoinduced mixed valence systems, i. e. those where the mixed valence core is absent in the ground state but created upon light absorption. The focus is on the utilization of photoinduced intervalence charge transfer bands, detected via transient absorption spectroscopy, as key tools to study fundamental phenomena like donor/acceptor inversion, hole delocalization, coexistence of excited states and excited state nature, together with applications in molecular electronics.

Investigation of the influence of clathrate hydrate crystals on the structuring of homeopathic high dilutions

High dilutions (HD) of drugs used in homeopathy are mostly too dilute to contain original drug molecules. But evidences support their specific biological and therapeutic effects. The reason behind this is thought to be water structure characteristic of the original drug. Spectroscopic studies indicate that the specific water structure in HDs can be resolved into free water molecules, hydrogen bonding strength of water hydroxyl, number of hydrogen bonds and clathrate hydrate crystals (CHC). HDs are prepared in EtOH water solution by serial dilution and mechanical agitation, and are called potencies. The objective of the present study is to further confirm the presence of CHCs in the two potencies of three drugs. Electronic spectra of the HDs of the potencies indicate two broad peaks and marked difference in intensities of absorption. Furior Transform Infrared (FT-IR) spectra of the test potencies and their control show difference in intensity shift and contour shape of OH stretching and bending bands. All the experimental data indicate the presence of CHCs in varying amounts in the test potencies.

High Dilutions of Drugs show Distinct Variation from each other in their Electronic Spectra

Drugs at high dilution (HD) produce therapeutic effect on man, animals and plants. Experimental evidence shows that free water molecules and hydrogen bond strength of OH groups constitute the physical basis of HDs which are otherwise devoid of original drug molecules. HDs are produced in aqueous EtOH by serial dilution of a substance with mechanical agitation or succussion in each step, and are called potencies. Three potencies 6 cH, 12 cH and 30 cH of two drugs Anacardium orientale and Natrum muriaticum(NaCl) and their mother tincture (MT) are used in this study. Electronic spectra of these MTs and potencies, all in 90% EtOH, were taken in the wavelength region of 190 nm ­350 nm. The objective is to find out any additional physical-chemical entities in potencies besides the aforesaid two factors. It was reported earlier that charge transfer (CT) interaction accompanies potentization of drugs. This study focused on the CT interaction. The results indicate that spectral pattern and absorbance intensities of the test samples vary from each other. Natm 6cH (absorbance 0.30 at 196.53nm), 12cH (abs. 0.06 at 196.53nm) and 30cH (abs. 1.32 at 196.5nm). Anac 6cH (abs. 0.33 at 203nm), 12cH (abs. 0.61 at 208nm) and 30cH (abs. 0.09 at 200.67nm). The spectrum of each potency shows two peaks. The 2nd peak at higher wave length belongs to CT interaction. Anac 6cH suc, 7cH unsuc. Insersections at 197.14nm with abs. 0.05, and 290nm with abs. 0.01. Anac 12cH suc, 13cH unsuc. Intersections at 196.93nm with abs. 0.06, and 273nm with abs. 0.00. Anac 30cH suc, 31cH unsuc. Intersections at 194.42nm with abs. -0.05, 238.03nm with abs. -0.01, 252.15nm with abs. -0.002, and 261nm with abs. 0.004. Natm 6cH suc, 7cH unsuc. Intersection at 199.44nm with Abs -0.11. Natm 12cH suc, 13cH unsuc. Instersection at 200.48nm with abs. -0.11. Natm 30cH suc, 31cH unsuc. Intersection at 204.24nm with abs. -0.08. Potentization involves CT interaction in consecutive potencies. Water and EtOH do not form a homogeneous mixture and have aggregates of EtOHand water molecules. CT interactions occur in these individual aggregates and are mostly inter molecular within EtOH or water. These aggregates vary from each other in the test samples. The spectra of test samples were analysed for margin of error (MOE). The MOE is very small (0.001-0.002%), and for this reason the difference between the spectra is significant. Besides that the intersection between consecutive spectra vary in number and position. It is concluded that water and EtOH aggregates and their relative distribution constitute additional physical-chemical basis of potencies.

CO2 Adsorption on PtCu Sub-Nanoclusters Deposited on Pyridinic N-Doped Graphene: A DFT Investigation.

To reduce the CO2 concentration in the atmosphere, its conversion to different value-added chemicals plays a very important role. Nevertheless, the stable nature of this molecule limits its conversion. Therefore, the design of highly efficient and selective catalysts for the conversion of CO2 to value-added chemicals is required. Hence, in this work, the CO2 adsorption on Pt4-xCux (x = 0-4) sub-nanoclusters deposited on pyridinic N-doped graphene (PNG) was studied using the density functional theory. First, the stability of Pt4-xCux (x = 0-4) sub-nanoclusters supported on PNG was analyzed. Subsequently, the CO2 adsorption on Pt4-xCux (x = 0-4) sub-nanoclusters deposited on PNG was computed. According to the binding energies of the Pt4-xCux (x = 0-4) sub-nanoclusters on PNG, it was observed that PNG is a good material to stabilize the Pt4-xCux (x = 0-4) sub-nanoclusters. In addition, charge transfer occurred from Pt4-xCux (x = 0-4) sub-nanoclusters to the PNG. When the CO2 molecule was adsorbed on the Pt4-xCux (x = 0-4) sub-nanoclusters supported on the PNG, the CO2 underwent a bond length elongation and variations in what bending angle is concerned. In addition, the charge transfer from Pt4-xCux (x = 0-4) sub-nanoclusters supported on PNG to the CO2 molecule was observed, which suggests the activation of the CO2 molecule. These results proved that Pt4-xCux (x = 0-4) sub-nanoclusters supported on PNG are adequate candidates for CO2 adsorption and activation.

High dilutions of a drug of COVID-19 origin show difference in ranks

High dilutions (HDs) of drugs, used in Homeopathy, are prepared in aqueous EtOH (ethanol) through serial dilution accompanying mechanical agitation or succussion, and are called potencies. The potencies from the rank 12 onwards are too dilute to contain any original drug molecules. Do the potency ranks show any difference from each other? Do serial dilution and succussion contribute to the difference in potency ranks? This study aims to address these two questions. The throat swab of a Covid-19 patient was preserved and diluted with aqueous EtOH 90% to prepare the mother tincture (MT) and five different potencies of Covid named Covidinum. These potencies and their solvent media were analysed by electronic and vibrational spectroscopy. Charge transfer (CT) and proton transfer interactions occur during preparation of the potencies. The FT-IR spectra of all the test samples after normalization show difference from each other with respect to O-H stretching and bending (v2) bands. Serial dilution and succussion contribute to the observed difference in ranks and CT interactions.

SERS and resonance Raman of 5-nitroisatin on silver - The distinction between the coordination and surface complexes.

Although Surface Enhanced Raman Spectroscopy (SERS) is a widespread technique with applications in several fields, the SERS effect is still not thoroughly understood due to the challenge in describing how the interaction between the analyte and the metallic surface contributes to the Raman signal enhancement. One approach to distinguish the charge transfer contribution from the metal to the molecule is the comparison of the coordination complex resonance Raman spectral features with the SERS spectra of the surface complex excited at different wavelengths. Herein, we investigated the molecule 5-nitroisatin, Nisa, its complex with a silver cation, Ag(Nisa), its anionic form, Nisa-, and the adsorbed species over Ag colloid, Nisa/AgNP, by resonance Raman and SERS, respectively. The data show that the resonance Raman spectrum of the coordination complex Ag(Nisa) is comparable to the SERS spectrum obtained out of resonance condition. However, when the SERS spectra of Nisa/AgNP at resonance condition is obtained, quite distinct chromophores are observed. The SERS enhancement profile suggests a charge transfer from the metal to molecule in the green region of the visible spectrum and evidences the higher complexity of the electronic transitions that take place within the surface complex. To support the experimental data, DFT and TDDFT calculations were performed for Nisa, Ag(Nisa), Nisa- and Nisa@Ag20 cluster.

Probing the Charge Transfer in a Frustrated Lewis Pair by Resonance Raman Spectroscopy and DFT Calculations.

A classical Lewis adduct derives from a covalent bond between a Lewis acid and a base. When the adduct formation is precluded by means of steric hindrance the association of the respective acid-base molecular system is defined as a frustrated Lewis pair (FLP). In this work, the archetypal FLP Mes3 P/B(C6 F5 )3 was characterized for the first time by resonance Raman spectroscopy, and the results were supported by density functional theory (DFT) calculations. The charge transfer nature of the lowest energy electronic transition, from phosphine to borane, was confirmed by the selective enhancement of the Raman bands associated to the FLP chromophore at resonance condition. Herein, we demonstrate the use of resonance Raman spectroscopy as a distinguished technique to probe the weak interaction involved in FLP chemistry.