The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4- dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G(d,p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations. © 2011 Elsevier B.V. All rights reserved.

NIKHIL GUCHHAIT

Chemistry

S JANA

S DALAPATI

S GHOSH

S KAR

University of Calcutta (informally known as Calcutta University or CU) is a collegiate public state university located in Kolkata, West Bengal, India.&nbsp;Within India it is recognized as a &quot;Five-Star University&quot; and accredited &quot;A&quot; Grade by National Assessment and Accreditation Council.

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The University of Calcutta has secured the Fifth position among the Universities of India in the prestigious &quot;Indian University Ranking 2019&quot; list, released by the NIRF of the Ministry of Human Resource Development, Government of India.

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It was established on 24 January 1857, and was one of the first institutions in Asia to be established as a multidisciplinary and Western-style university. Its alumni and faculty include several heads of state, heads of government, social reformers, prominent artists, only academy award winner and Dirac medal winner in India, many Fellows of the Royal Society and five Nobel laureates as of 2019 which is highest in South Asia.

University Of Calcutta

Journal of Molecular Structure

We report the synthesis and photophysical properties of a coumarin based probe (1E)-1-(1-(7-(diethylamino)-2-oxo-2H-chromen-3-yl) ethylidene) thiosemicarbazide (DIDOT). DIDOT shows a polarity dependent change in the emission maxima in the solution phase. This is explained by the increased dipole moment in the excited state by an intramolecular charge transfer (ICT) process. DIDOT can successfully detect Zn(ii) in aqueous methanol by a shift in the charge transfer emission maxima from approximately 506 to approximately 535 nm. This shift led to a change in the color of the emission from green to yellow under UV-light. The mechanism of Zn(ii) detection has been delineated using electrospray ionization-mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FTIR) and fluorescence time resolved studies coupled with theoretical calculations. The increment in the charge transfer in the Zn(ii) complex of DIDOT over the bare receptor as a consequence of conformational locking was determined to be the underlying cause of the cation detection phenomenon. The limit of detection and binding constant values of DIDOT towards Zn(ii) were approximately 3 × 10-8 M and 2.35 × 105 M-1 respectively. Finally, the practical utility of DIDOT has been demonstrated by successful detection and quantification of Zn(ii) in spiked water samples. © 2019 The Royal Society of Chemistry and Owner Societies.

Photochemical and Photobiological Sciences

Evaluating the merit of a diethylamino coumarin-derived thiosemicarbazone as an intramolecular charge transfer probe: Efficient Zn(II) mediated emission swing from green to yellow

We present a detailed photophysical properties of a synthesized charge transfer (CT) molecule (2E, 4E)-ethyl 2-cyano-5-(4-(dimethylamino) phenyl) penta-2, 4-dienoate (ECDPPD) in bulk medium and its spectral modulation inside β-Cyclodextrin cavity. Enhancement of acceptor strength of 4-(dimethylamino) cinnamaldehyde by replacing the moderate acceptor in the form of a Formyl group by two acceptors known to display greater electron withdrawing ability along with extra conjugation which may be responsible for higher dipole moment both in ground as well as in excited state. The observed excited CT process and its solvent polarity dependent emissive properties is due to simply increasing the ‘end-to-end’ length between donor and acceptor along with introduction of two different acceptors in the same site. Low fluorescence quantum yield and shorter fluorescence lifetime is due to the operation of active non-radiative channels through flexible bonds supported by viscosity and temperature dependent spectral measurement. The molecule ECDPPD easily interacts with β-CD with the formation of inclusion complex with a definite stoichiometry where the photophysics are modulated and hence can be used as fluorescence microenvironment reporter for example to evaluate the polarity as well as the micro viscosity of various regions of protein and other bimolecular systems. © 2018 Elsevier B.V.

Journal of Photochemistry and Photobiology A: Chemistry

Influence of acceptor strength on photoinduced charge transfer process in a newly designed molecule in bulk solvent and in Î²-CD microenvironment

In this work, we report intramolecular charge transfer (ICT) suppressed excited state intramolecular proton transfer (ESIPT) process in 4-(diethylamino)-2-hydroxybenzaldehyde (DEAHB). Photophysical properties of DEAHB have been extensively studied in different solvents with varying pH, polarity, and hydrogen bonding capability of the solvent using steady state and time-resolved spectroscopy. To establish the competition between the ICT and ESIPT processes in DEAHB, we have synthesized and studied the photophysical properties of 4-(diethylamino)-2-methoxybenzaldehyde (DEAMB) molecule where only the charge transfer process has been observed. Recently, we have reported simple Schiff base molecules (J. Phys. Chem. A 2012, 116, 10948) formed by condensation of DEAHB and hydrazine (5-(diethylamino)-2-[(4-(diethylamino) benzylidene)hydrazonomethyl]phenol (DDBHP) and N,N′-bis(4-N,N- (diethylamino)salisalidene)hydrazine (DEASH)), where charge transfer is assisted by the proton transfer process. In the present case, the DEAHB molecule shows the reverse phenomenon; i.e., charge transfer is suppressed by the proton transfer process. Comparing the photophysical properties of DEAHB with DEAMB it is also found that ICT process in DEAHB is suppressed by the ESIPT process. © 2013 American Chemical Society.

Journal of Physical Chemistry A

Excited state intramolecular charge transfer suppressed proton transfer process in 4-(diethylamino)-2-hydroxybenzaldehyde

The molecule methyl-2-aminonicotinate (2-MAN) does not exhibit excited state intramolecular proton transfer (ESIPT), but its derivative 4-amino-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester (AMPCE), widely used in the preparation of pyrimidopyrimidines as a protein kinase inhibitor, does exhibit ESIPT. Increasing acidic and basic character at the proton donor and proton acceptor sites by adding functional groups is found to be responsible for the large Stokes shifted ESIPT emission (Δν = 12 706 cm-1) in AMPCE. The photophysics of AMPCE have been explored on the basis of steady state and time resolved spectral measurements, quantum yield calculation with variation of polarity, as well as hydrogen bonding ability of solvents. Experimental findings have been correlated with the calculated structure and potential energy surfaces based on the intramolecular proton transfer model obtained by density functional theory (DFT). Properties based on the calculated excited state surfaces generated in vacuo and methanol solvent using time dependent density functional theory (TDDFT) and time dependent density functional theory polarized continuum model (TDDFT-PCM), respectively, show good agreement with the experimental findings. HOMO and LUMO diagrams also support the favorable ESIPT process in the first excited state potential energy surface. © 2013 The Royal Society of Chemistry and Owner Societies.

Functional group induced excited state intramolecular proton transfer process in 4-amino-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester: A combined spectroscopic and density functional theory study

Photophysical properties of an anthracene derivative 9-methyl anthroate (9-MA) have been investigated using absorption and emission spectroscopy, in combination with quantum chemical calculations. Solvatochromic effects on the Stokes shifted emission band clearly demonstrate the highly polar character of the excited state, which is also supported by the enhancement of dipole moment of the molecule upon photoexcitation. The emission band has been found to be dependent on polarity and hydrogen-bonding ability of the solvents. Multiple linear regression analysis method has been utilized to rationalize the effect of hydrogen bonding interaction on the emissive state, which was further confirmed by the analysis of the non-radiative decay constants and urea induced H-bonding disruption study. The experimental results correlate well with theoretical predictions obtained via density functional theory (DFT). © 2013 Elsevier B.V. All rights reserved.

Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

Solvent modulated photophysics of 9-methyl anthroate: Exploring the effect of polarity and hydrogen bonding on the emissive state

A donor acceptor substituted aromatic system 5-(4-dimethylamino-phenyl)- penta-2,4-dienoic acid (DMAPPDA) has been synthesized and its spectral properties have been explored on the basis of steady state absorption and fluorescence spectroscopy. Spectral features point largely towards a possible occurrence of photoinduced intramolecular charge transfer process from the donor NMe2 group to the acceptor acid group. Solvent dependency of the large Stokes' shifted emission band and the calculated large excited state dipole moment support the polar character of the charge transfer excited state. Quantum yield calculations and effect of addition of acid and base on the steady state spectra were also performed to further scrutinize the excited state CT character. © 2010 Elsevier B.V. All rights reserved.

Photoinduced intramolecular charge transfer phenomena in 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid

Intramolecular charge transfer (ICT) reaction has been investigated in 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid methyl ester (DPDAME) using spectroscopic techniques. The molecule DPDAME shows local emission in non-polar solvent and dual emission in polar solvents. Solvatochromic effects on the Stokes shifted emission band clearly demonstrate the charge transfer character of the excited state. Quantum chemical calculations have been performed at Hartree-Fock (HF) and density functional theoretical (DFT) levels to correlate the experimental findings. Potential energy curves (PECs) for the ICT reaction have been evaluated along the donor twist angle at DFT and time dependent density functional theory (TDDFT) levels for the ground and excited states, respectively, using B3LYP hybrid functional and 6-31G** basis set. The solvent effects on the spectral properties have been explored theoretically at the same level with time dependent density functional theory-polarized continuum model (TDDFT-PCM) and the theoretical results are found to well substantiate the solvent polarity dependent Stokes shifted emission of DPDAME. Huge enhancement of dipole moment (Δμ=16.42 D) of the molecule following photoexcitation dictates the highly polar character of the excited state. Although elucidation of PECs does not exactly predict the operation of ICT according to twisted intramolecular charge transfer (TICT) model in DPDAME, lowering of vertical transition energy as a function of the donor twist coordinate scripts the occurrence of red shifted emission as observed experimentally. © 2010 Elsevier B.V. All rights reserved.

Journal of Luminescence

Evidence for excited state intramolecular charge transfer reaction in donor-acceptor molecule 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid methyl ester: Experimental and quantum chemical approach

In this study, spectroscopic properties of (E)-3-(4-dimethylamino-naphthalen-1-yl)-acrylic acid (DMANAA) have been explored using absorption and emission spectroscopy in combination with quantum chemical calculations. In addition to the local emission, the molecule shows a red-shifted emission from the charge transfer state. The charge transfer emission band is found to be dependent on polarity and hydrogen-bonding ability of the solvents. This photo-induced charge transfer process has been explored theoretically at Density Functional Theory level using twisted intramolecular charge transfer model. Structural calculations and potential energy surfaces along the donor twist coordinate done by Density Functional Theory correlate well with the spectroscopic observations. Addition of metal ions to DMANAA solutions in acetonitrile solvent shows progressive quenching of the charge transfer band and growth of a blue-shifted band, making way for its use as a good fluorosensor for various metal ions. © 2009 Elsevier B.V. All rights reserved.

Photo-induced charge transfer emission in (E)-3-(4-dimethylamino-naphthalen-1-yl)-acrylic acid and its use as metal ions fluorosensor

Sensitivity of the charge-transfer (CT) band of the fluorescence probe (E)-3-(4-methylaminophenyl)acrylic acid methyl ester (MAPAME) towards the polarity of its immediate environment is employed to investigate the binding interaction of the probe with bovine serum albumin (BSA) and uncoiling of BSA by the denaturants urea and sodium dodecyl sulfate micelles. Binding of the probe with BSA produces a blue shift and enhanced intensity of the CT emission band which clearly point toward a decrease in polarity of the immediate environment of MAPAME. This is expected, since binding with BSA moves the probe from a polar water environment to a much less polar, hydrophobic protein interior, where the CT band is expected to be blue-shifted. Higher intensity arises due to fewer non-radiative decay paths available to the probe in the hydrophobic protein environment. Chemically induced unfolding of BSA by urea and sodium dodecyl sulfate is tracked by monitoring the induced spectral changes of the protein-bound probe MAPAME. Red-edge excitation shift or REES, fluorescence resonance energy transfer (FRET) and anisotropy measurements are used to investigate and monitor these binding and unfolding processes. © 2009 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

ChemPhysChem

Chemically induced unfolding of bovine serum albumin by urea and sodium dodecyl sulfate: A spectral study with the polarity-sensitive charge-transfer fluorescent probe (E)-3-(4-methylaminophenyl)acrylic acid methyl ester

Steady state absorption, fluorescence and time resolved fluorescence spectroscopy have been used for studying the photoinduced intramolecular charge transfer reaction in (E)-3-(4-methylamino-phenyl)-acrylic acid ethyl ester (MAPAEE). The title molecule shows dual emission due to high energy local and a low energy charge transfer emission. Depending on the nature of solvent the red shifted emission band shows good correlation with the solvent polarity parameter, ET(30) parameter and hydrogen bonding parameter. Quantum chemicals calculations by density functional theory predict that a stabilized twisted intramolecular charge transfer excited state generated either by twisting of the donor group ({single bond}NHMe) or the acceptor (- = {single bond}COOEt) group is responsible for the red shifted charge transfer emission. The solvent polarity dependent red shifted emission from the excited charge transfer state of MAPAEE has been used as fluorosensor to study bovine serum albumin proteinous and sodium dodecyl sulphate micellar microenvironment. © 2008 Elsevier B.V. All rights reserved.

Dual emission from (E)-3-(4-methylamino-phenyl)-acrylic acid ethyl ester (MAPAEE) and its application as fluorescence probe for studying micellar and protein microenvironment

Excited state charge transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

Journal	Data powered by TypesetJournal of Molecular Structure
Publisher	Data powered by TypesetELSEVIER SCIENCE BV
ISSN	0022-2860
Open Access	No