Revealing the biradicaloid nature inherited in the derivatives of thieno[3,4-c][1,2,5]thiadiazole: a computational study.

Computational studies were performed on non-classical thieno[3,4-c][1,2,5] thiadiazole and its pi donor derivatives (TT dyes) so as to delineate the factors responsible for their near-infrared (NIR) absorption. For all dyes except the unsubstituted bare dye, adiabatic singlet-triplet energy gaps (estimated through the ΔSCF procedure using the B3LYP and M062X DFT methods and SFTDDFT with the 5050 functional) were less than 1eV. Percentage calculations of the biradicaloid character suggested a moderate biradicaloid nature in all derivatives. There was a resemblance between the frontier molecular orbital (MO) picture of the TT bicyclic ring and the degenerate non-bonding molecular orbitals of Trimethyleneethane (TME, a known biradical). Inter-fragment charge transfer analysis revealed not only a considerable donation of charge to the central ring (Acceptor, TT part) but also substantial charge redistribution within the ring itself. From these results, it was inferred that NIR absorption, in these dyes, was due to: (1) a reduced HOMO-LUMO gap (HLG) as a TME biradical substructure forms its chromophoric part; and (2) charge transfer from the donor substituents. The non-bonding nature of the S atom, in the bare dye, with its neighbouring N/C atom (of the highest occupied π-MOs), led to an examination of its electronic structure using the ab initio valence bond method. The relatively large weight and energetic stability of the biradicaloid VB structures compared to those of the ylidic structures clearly disclosed the importance of biradicaloid structures in the overall resonance of the bare dye. Their utility as singlet fission materials was screened using singlet and triplet energy-based molecular structure activity criteria. The results were encouraging, demanding experiments to reaffirm the materials' usefulness.

Experimental and theoretical insights on the effect of solvent polarity on the photophysical properties of a benzanthrone dye.

Benzanthrone derivatives show interesting solvent dependent photophysical properties. Understanding of their photophysical properties is essential for developing the fluorescence probes based on benzanthrone derivatives. The photophysical properties of 3-(N'-chlorophenyl)piperazino-7H-benzo[de]anthracen-7-one [ClPh-PBA] molecule are reported in different solvents and solvent mixtures. The change in Stokes shift, quantum yield, fluorescence life time and radiative rate constants as a function of solvent polarity shows that the Intermolecular Charge Transfer (ICT) is affected by solvent polarity and hydrogen bonding. The quantum yield and fluorescence life time values decrease and the nonradiative decay rate constant (knr) values are observed to be higher in polar solvents. The weak emission of ClPh-PBA in polar solvents is primarily due to the non-radiative torsional motion of the chlorophenyl group around benzanthrone moiety. The torsional motion of chlorophenyl group at the remote nitrogen around benzanthrone moiety is also evident from TDDFT calculations performed using B3LYP/6-311+ G (d, p) basis set. The ground state and excited state dipole moments, absorption and emission maxima (nm) along with other quantum chemical parameters are obtained using B3LYP/6-311+ G (d, p) basis set. The experimental and theoretical results follow the similar trends.

Understanding the interaction of carbon quantum dots with CuO and Cu2O by fluorescence quenching.

In spite copper oxide being one of the essential micronutrient, copper oxide in its nano size is found to be toxic in nature; this instigates for the detection of copper oxides in trace levels. In the present study, we demonstrate simple cost effective detection method for CuO/Cu2O using carbon quantum dots (CQD) by fluorescence quenching technique. CuO/Cu2O nanoparticles are synthesised by mere variation of fuel ratio by solution combustion technique. The resulting oxides are characterized by various analytical and spectroscopic techniques. Powder X- ray diffraction (PXRD) results reveals that samples prepared with oxidizer to fuel (O/F) ratios 1:1, 1:1.5 and 1:2 showed pure nano CuO, major CuO phase (minor Cu2O) and major Cu2O phase (minor CuO) respectively. Further, the samples prepared using 1:1 O/F ratio and calcinated at 700 °C showed highly crystalline CuO phase. In order to study the interaction of CuO/ Cu2O with CQDs the fluorescence quenching method has been employed. The bimolecular quenching rate constants for the samples prepared with different O/F ratios have been measured. The interaction between CQDs and copper oxides, indicates fluorescence quenching greatly depends on the oxidation state of the copper oxide and can be a promising method for detecting CuO/Cu2O through CQDs.

Photophysical properties of benzanthrone derivatives: effect of substituent, solvent polarity and hydrogen bonding.

Benzanthrone derivatives are potential fluorescent probes for various chemical and biological environments. A mechanistic understanding of their photophysical properties is pivotal for designing an efficient fluorescence sensor based on the benzanthrone framework. In this study, we report on the effect of chemical substitution on the photophysical properties of two benzanthrone derivatives, namely, 3-(N'-methyl)-piperazino-7H-benzo[de]anthracen-7-one [Me-PBA] and 3-(N'-phenyl)-piperazino-7H-benzo[de]anthracen-7-one [Ph-PBA] in different solvents and solvent mixtures of varying polarities and proticities. Both benzanthrone derivatives show interesting solvent-dependent photophysical properties. Although both derivatives exhibit strong intramolecular charge transfer (ICT) characteristics in the excited state, the extent of the charge transfer is significantly influenced by the nature of the chemical substitution. Modulation of photophysical parameters as a function of solvent properties led us to propose that ICT is affected by solvent polarity and hydrogen bonding. From the viscosity effect, it is revealed that the weaker emission of Ph-PBA compared to Me-PBA in polar solvents is primarily due to the non-radiative torsional motion of the phenyl group in the former derivative. In protic solvents, intermolecular hydrogen bonding imparts strong non-radiative deactivation to both derivatives, thus rendering a weak fluorescence yield.

Green and Cost Effective Synthesis of Fluorescent Carbon Quantum Dots for Dopamine Detection.

Carbon quantum dots (CQDs) due to its high fluorescent output is evolving as novel sensing material and is considered as future building blocks for nano sensing devices. Hence, in this investigation we report microwave assisted preparation and multi sensing application of CQDs. The microwave derived CQDs are characterized by Dynamic Light Scattering (DLS) experiment and Fourier Infrared spectra (FTIR) to investigate the size distribution and chemical purity respectively. Fluorescent emission spectra recorded at varying pH shows varying fluorescence emission intensities. Further, emission spectra recorded at different temperatures shows that fluorescence emission of CQDs greatly depends on temperature. Therefore, we demonstrate the pH and temperature sensing characteristics of CQDs by fluorescence quenching behaviour. In addition, the interaction and sensing behaviour of CQDs for dopamine is also presented in this work with a detection limit of 0.2 mM. The steady state and time-resolved methods have been employed in fluorescence quenching methods for sensing dopamine through CQDs at room temperature. The bimolecular quenching rate constants for different concentration have been measured. The interaction between CQDs and dopamine indicates fluorescence quenching method is an elegant process for detecting dopamine through CQDs.

Solvatochromic study of 3-N-(N'-methylacetamidino)benzanthrone and its interaction with dopamine by the fluorescence quenching mechanism.

The change in photophysical properties of the organic molecule due to solvatochromic effect caused by different solvent environments at room temperature gives information about the dipole moments of 3-N-(N'-methylacetamidino)benzanthrone (3-MAB). The quantum yield, fluorescence lifetime of 3-MAB was measured in different solvents to calculate radiative and non-radiative rate constants. The results revealed that the excited state dipole moment (µe ) is relatively larger compared to the ground state dipole moment (µg ), indicating the excited state of the dye under study is more polar than the ground state and the same trend is noticed with theoretical calculations performed using the CAM-B3LYP/6-311+G(d,p) method. Further, the study on preferential solvation was carried out for 3-MAB dye in ethyl acetate-methanol solvent mixture. The fluorescence quenching method has been employed for the detection of dopamine using 3-MAB as fluorescent probe, using steady-state and time resolved methods at room temperature. The method enables dopamine in the micro molar range to be detected. Also, an attempt to verify the quenching process by employing different models has been tried. Various rate parameters are measured using these models, our results indicates the quenching process is diffusion limited.

A combined spectroscopic and TDDFT investigation of the solute-solvent interactions of two coumarin derivatives.

The UV/Vis absorption and fluorescence characteristics of 3-cyano-7-hydroxycoumarin [CHC] and 7-amino-4-methyl-3-coumarinylacetic acid [AMCA-H] were studied at room temperature in several neat solvents and binary solvent mixtures of 1,4-dioxane/acetonitrile. The effects of solvent on the spectral properties are analyzed using single and multi-parameter solvent polarity scales. Both general solute/solvent interactions and hydrogen bond interactions are operative in these systems. The solvation of CHC and AMCA-H dyes in 1,4-dioxane/acetonitrile solvent mixtures has been studied. The solutes CHC and AMCA-H are preferentially solvated by acetonitrile and a synergistic effect is observed for both molecules in dioxane/acetonitrile solvent mixtures. In addition, using the solvatochromic method the ground- and the excited-state dipole moments of both the dyes were calculated. The ground- and excited-state dipole moments, absorption and emission maxima and HOMO-LUMO gap were also estimated theoretically using B3LYP/6-311+ G (d,p) level of theory in the gaseous phase, dioxane and acetonitrile solvents. Furthermore, changes in dipole moment values were also calculated using the variation of Stokes shift with the molecular-microscopic empirical solvent polarity parameter ( ETN). The observed excited-state dipole moments are larger than their ground-state counterparts, indicating a substantial redistribution of the electron densities in a more dipolar excited state for both coumarins investigated.

Estimation of the ground and the first excited singlet-state dipole moments of 1,4-disubstituted anthraquinone dyes by the solvatochromic method.

The both, ground-state (mu(g)) and the excited-state (mu(e)) dipole moments of three 1,4-disubstituted anthraquinones, namely 1,4-diaminoanthracene-9,10-dione (1,4-DAAQ), 1-amino-4-hydroxyanthracene-9,10-dione (1,4-AHAQ), and 1,4-dihydroxyanthracene-9,10-dione (1,4-DHAQ) were estimated in binary solvent mixtures (methylcyclohexane-ethyl acetate and ethyl acetate-acetonitrile). The dipole moments (mu(g) and mu(e)) were estimated from Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet, McRae, and Suppan equations by using the variation of Stokes shift with the solvent's relative permittivity and refractive index. The ground-state dipole moments were also calculated theoretically by Gaussian 03 software using B3LYP/6-31 G* level of theory. Further, the change in dipole moment values Deltamu were also calculated by using the variation of Stokes shift with the molecular-microscopic empirical solvent polarity parameter (E(T)(N)). The excited-state dipole moments observed are larger than their ground-state counterparts, indicating a substantial redistribution of the pi-electron densities in a more polar excited state for all the molecules investigated.

Estimation of first excited singlet-state dipole moments of aminoanthraquinones by solvatochromic method.

The ground state (micro(g)) and the excited state (micro(e)) dipole moments of three substituted anthraquinones, namely 1-aminoanthracene-9,10-dione (AAQ), 1-(methylamino)anthracence-9,10-dione (MAQ) and 1,5-diaminoanthracene-9,10-dione (DAQ) were estimated in various solvents. The dipole moments (micro(g) and micro(e)) were estimated from Lippert, Bakhshiev, Kawski-Chamma-Viallet, McRae and Suppan equations by using the variation of Stokes shift with the solvent dielectric constant and refractive index. The excited state dipole moments were also calculated by using the variation of Stokes shift with microscopic solvent polarity parameter (Epsilon(T)(N)). It was observed that dipole moment values of excited states (micro(e)) were higher than corresponding ground state values (micro(g)), indicating a substantial redistribution of the pi-electron densities in a more polar excited state for all the molecules investigated.