scholarly journals Push-Pull Chromophores Based on the Naphthalene Scaffold: Potential Candidates for Optoelectronic Applications

Materials ◽  
2019 ◽  
Vol 12 (8) ◽  
pp. 1342 ◽  
Author(s):  
Corentin Pigot ◽  
Guillaume Noirbent ◽  
Thanh-Tuân Bui ◽  
Sébastien Péralta ◽  
Didier Gigmes ◽  
...  
Keyword(s):  
Theoretical Calculations ◽  
Charge Transfer Band ◽  
Photophysical Properties ◽  
Polar Solvents ◽  
Visible Absorption ◽  
Synthetic Procedure ◽  
Multistep Procedure ◽  
Uv Visible ◽  
Electron Withdrawing Group ◽  
Positive Solvatochromism

A series of ten push-pull chromophores comprising 1H-cyclopenta[b]naphthalene-1,3(2H)-dione as the electron-withdrawing group have been designed, synthesized, and characterized by UV-visible absorption and fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. The solvatochromic behavior of the different dyes has been examined in 23 solvents and a positive solvatochromism has been found for all dyes using the Kamlet-Taft solvatochromic relationship, demonstrating the polar form to be stabilized in polar solvents. To establish the interest of this polyaromatic electron acceptor only synthesizable in a multistep procedure, a comparison with the analog series based on the benchmark indane-1,3-dione (1H-indene-1,3(2H)-dione) has been done. A significant red-shift of the intramolecular charge transfer band has been found for all dyes, at a comparable electron-donating group. Parallel to the examination of the photophysical properties of the different chromophores, a major improvement of the synthetic procedure giving access to 1H-cyclopenta[b]naphthalene-1,3(2H)-dione has been achieved.

scholarly journals PYRENE EMISSION FROM MONOLAYERS "CLICKED" ONTO QUARTZ

2013 ◽  
Vol 01 (01) ◽  
pp. 1250007
Author(s):  
HONGYAN SONG ◽  
SERGEY GORELIK ◽  
JONATHAN HOBLEY ◽  
JIEXUN LI ◽  
AÏCHA BOUDHAR ◽  
...  
Keyword(s):  
Photoelectron Spectroscopy ◽  
Surface Coverage ◽  
Charge Transfer Band ◽  
Photophysical Properties ◽  
High Surface ◽  
Excimer Emission ◽  
Excitation Spectra ◽  
Visible Absorption ◽  
Molecular Monolayers ◽  
A Charge

A series of quartz surfaces were modified with a series of crosslinkers and functional groups in order to obtain an azide-terminated monolayer, which was then used to immobilize pyrene onto the surface via alkyne-azide "click" chemistry. During the course of the immobilization, different ratios of tert-butyl diphenyl chlorosilane were used to control the distribution and hence the photophysical properties of the pyrene on the surface. The preparative surface reactions and photophysical properties were investigated with contact angle, X-ray photoelectron spectroscopy, UV-visible absorption and emission spectroscopy. High surface coverage was achieved of just under 1molecule per nm2. At this coverage all emission from the pyrene was in the form of excimer emission. Excimer emission dominated at all surface coverages greater than 0.45 molecules per nm2. Below this coverage the monomer emission could also be observed. The conclusions that can be drawn are important for understanding the interactions of neighboring molecules in molecular monolayers. Our results suggest that at high surface coverage a substantial number of the pyrene molecules are already close enough to their neighbors that pairs of them can be directly excited to form excimer with no requirement for diffusion. This can be stated because the long wavelength end of the pyrene absorption and excitation spectra show a broad tail that is assigned to a charge transfer band resulting from an electron being directly transferred from a ground state pyrene to a neighboring pyrene molecule. Furthermore, absorption spectra shifts also indicate that the pyrene molecules undergo some interactions on the surface when they are closely packed.

scholarly journals A Highly Selective Economical Sensor for 4-Nitrophenol

2021 ◽  
Vol 2 (3) ◽  
pp. 506-520
Author(s):  
Thuy Le ◽  
Yusuf Khan ◽  
Nicholas Speller ◽  
Mujeebat Bashiru ◽  
Samantha Macchi ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Aqueous Medium ◽  
Limit Of Detection ◽  
Photophysical Properties ◽  
Sodium Fluorescein ◽  
Dynamic Quenching ◽  
Visible Absorption ◽  
Fluorescence Spectrophotometry ◽  
Uv Visible ◽  
Static And Dynamic Quenching

Herein, an inexpensive commercially available sensor is presented for the detection of 4-nitrophenol (4NP) pollutant. Sodium fluorescein (NaFl) is used as a sensor to detect trace amounts of 4NP in acetonitrile (MeCN). The photophysical properties of NaFl were studied in two different solvents, MeCN (aprotic) and water (protic), with varying concentrations of different nitroaromatics using UV-visible absorption and fluorescence spectrophotometry. In an aqueous medium, photophysical properties of NaFl did not change in the presence of nitroaromatics. However, examination of the photodynamics in MeCN demonstrated that NaFl is extremely sensitive to 4NP (limit of detection: 0.29 µg/mL). This extreme specificity of NaFl towards 4NP when dissolved in MeCN, as compared to other nitroaromatics, is attributed to hydrogen bonding of 4NP with NaFl in the absence of water, resulting in both static and dynamic quenching processes. Thus, NaFl is demonstrated as a simple, inexpensive, sensitive, and robust optical turn off sensor for 4NP.

scholarly journals 2,4-Bis(arylethynyl)-9-chloro-5,6,7,8-tetrahydroacridines: synthesis and photophysical properties

2021 ◽  
Vol 17 ◽  
pp. 1629-1640
Author(s):  
Najeh Tka ◽  
Mohamed Adnene Hadj Ayed ◽  
Mourad Ben Braiek ◽  
Mahjoub Jabli ◽  
Noureddine Chaaben ◽  
...  
Keyword(s):  
Density Functional ◽  
Photophysical Properties ◽  
Chemical Properties ◽  
Efficient Synthesis ◽  
One Pot ◽  
Visible Absorption ◽  
Functional Theory ◽  
Uv Visible ◽  
Physical And Chemical ◽  
And Chemical Properties

Acridine derivatives have attracted considerable interest in numerous areas owing to their attractive physical and chemical properties. Herein, starting from readily available anthranilic acid, an efficient synthesis of 2,4-bis(arylethynyl)-9-chloro-5,6,7,8-tetrahydroacridine derivatives was accomplished via a one-pot double Sonogashira cross-coupling method. The UV-visible absorption and emission properties of the synthesized molecules have been examined. Additionally, theoretical studies based on density functional theory (DFT/B3LYP/6-31G(d)) were carried out.

Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety

2015 ◽  
Vol 19 (07) ◽  
pp. 819-829 ◽  
Author(s):  
Xu Liang ◽  
Li Xu ◽  
Minzhi Li ◽  
John Mack ◽  
Justin Stone ◽  
...  
Keyword(s):  
Electronic Structures ◽  
Magnetic Circular Dichroism ◽  
Theoretical Calculations ◽  
Free Base ◽  
Facile Synthesis ◽  
Visible Absorption ◽  
H Nmr ◽  
Uv Visible ◽  
Porphyrin Dimers ◽  
Porphyrin Dimer

A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1 H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.

scholarly journals Synthesis and Optical Characterization of Mixed Ligands Beryllium Complexes for Display Device Applications

2015 ◽  
Vol 2015 ◽  
pp. 1-7 ◽  
Author(s):  
Vandna Nishal ◽  
Devender Singh ◽  
Raman Kumar Saini ◽  
Vijeta Tanwar ◽  
Shri Bhagwan ◽  
...  
Keyword(s):  
Metal Complexes ◽  
Theoretical Calculations ◽  
Photophysical Properties ◽  
Frontier Molecular Orbital ◽  
Orbital Energy ◽  
Resonance Spectroscopy ◽  
Display Device ◽  
Visible Absorption ◽  
Good Thermal Stability ◽  
Beryllium Complexes

Synthesis and photoluminescent behaviour of mixed ligand based beryllium complexes with 2-(2-hydroxyphenyl)benzoxazole (HPB) and 5-chloro-8-hydroxyquinoline (Clq) or 5,7-dichloro-8-hydroxyquinoline (Cl2q) or 2-methyl-8-hydroxyquinoline (Meq) or 8-hydroxyquinoline (q) are reported in this work. These complexes, that is, [BeHPB(Clq)], [BeHPB(Cl2q)], [BeHPB(Meq)], and [BeHPB(q)], were prepared and their structures were confirmed by elemental analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and thermal analysis. The beryllium complexes exhibited good thermal stability up to ~300°C temperature. The photophysical properties of beryllium complexes were studied using ultraviolet-visible absorption and photoluminescence emission spectroscopy. The complexes showed absorption peaks due toπ-π∗andn-π∗electronic transitions. The complexes emitted greenish blue light with peak wavelength at 496 nm, 510 nm, 490 nm, and 505 nm, respectively, consisting of high intensity. Color tuning was observed with changing the substituents in quinoline ring ligand in metal complexes. The emitted light had Commission Internationale d’Eclairage color coordinates values atx=0.15andy=0.43for [BeHPB(Clq)],x=0.21andy=0.56for [BeHPB(Cl2q)],x=0.14andy=0.38for [BeHPB(Meq)],x=0.17andy=0.41for [BeHPB(q)]. Theoretical calculations using DFT/B3LYP/6-31G(d,p) method were performed to reveal the three-dimensional geometries and the frontier molecular orbital energy levels of these synthesized metal complexes.

Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Properties and Molecular Nonlinearity

2020 ◽  
Author(s):  
Zeyu Liu ◽  
Shugui Hua ◽  
Tian Lu ◽  
Ziqi Tian
Keyword(s):  
Optical Properties ◽  
Rational Design ◽  
Rayleigh Scattering ◽  
Function Analysis ◽  
Theoretical Calculations ◽  
Photophysical Properties ◽  
Optical Nonlinearity ◽  
Nonlinear Properties ◽  
Photoelectric Performance ◽  
Wave Function Analysis

Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlinear properties observed in the experiment can be perfectly replicated, our theoretical calculations explored the essential characteristics of the optical properties of the mesoionic compounds with different electron-donating groups at the level of electronic structures through various wave function analysis methods. The influence of the electron-donating ability of the donor on the optical properties of the molecules and the contribution of the mesoionic ring moiety to their optical nonlinearity are clarified, which have not been reported by any research so far. This work will help people understand the nature of optical properties of mesoionic-based molecules and provide guidance for the rational design of molecules with excellent photoelectric performance in the future.

A Unified Model for Photophysical and Electro-Optical Properties of Green Fluorescent Proteins

2019 ◽  
Author(s):  
Chi-Yun Lin ◽  
Matthew Romei ◽  
Luke Oltrogge ◽  
Irimpan Mathews ◽  
Steven Boxer
Keyword(s):  
Driving Force ◽  
Fluorescent Protein ◽  
Charge Transfer Band ◽  
Photophysical Properties ◽  
Polymethine Dyes ◽  
Emission Rates ◽  
Unified Framework ◽  
Underlying Factor ◽  
Green Fluorescent ◽  
Protein Environment

Green fluorescent protein (GFPs) have become indispensable imaging and optogenetic tools. Their absorption and emission properties can be optimized for specific applications. Currently, no unified framework exists to comprehensively describe these photophysical properties, namely the absorption maxima, emission maxima, Stokes shifts, vibronic progressions, extinction coefficients, Stark tuning rates, and spontaneous emission rates, especially one that includes the effects of the protein environment. In this work, we study the correlations among these properties from systematically tuned GFP environmental mutants and chromophore variants. Correlation plots reveal monotonic trends, suggesting all these properties are governed by one underlying factor dependent on the chromophore's environment. By treating the anionic GFP chromophore as a mixed-valence compound existing as a superposition of two resonance forms, we argue that this underlying factor is defined as the difference in energy between the two forms, or the driving force, which is tuned by the environment. We then introduce a Marcus-Hush model with the bond length alternation vibrational mode, treating the GFP absorption band as an intervalence charge transfer band. This model explains all the observed strong correlations among photophysical properties; related subtopics are extensively discussed in Supporting Information. Finally, we demonstrate the model's predictive power by utilizing the additivity of the driving force. The model described here elucidates the role of the protein environment in modulating photophysical properties of the chromophore, providing insights and limitations for designing new GFPs with desired phenotypes. We argue this model should also be generally applicable to both biological and non-biological polymethine dyes.<br>

scholarly journals Photophysical Properties of Protoporphyrin IX, Pyropheophorbide-a, and Photofrin® in Different Conditions

2021 ◽  
Vol 14 (2) ◽  
pp. 138
Author(s):  
Bauyrzhan Myrzakhmetov ◽  
Philippe Arnoux ◽  
Serge Mordon ◽  
Samir Acherar ◽  
Irina Tsoy ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Photophysical Properties ◽  
Protoporphyrin Ix ◽  
Fluorescence Emission ◽  
Solvent Polarity ◽  
Visible Absorption ◽  
Light Dosimetry ◽  
Time Resolved ◽  
Pyropheophorbide A ◽  
Influence Of Solvent

Photodynamic therapy (PDT) is an innovative treatment of malignant or diseased tissues. The effectiveness of PDT depends on light dosimetry, oxygen availability, and properties of the photosensitizer (PS). Depending on the medium, photophysical properties of the PS can change leading to increase or decrease in fluorescence emission and formation of reactive oxygen species (ROS) especially singlet oxygen (1O2). In this study, the influence of solvent polarity, viscosity, concentration, temperature, and pH medium on the photophysical properties of protoporphyrin IX, pyropheophorbide-a, and Photofrin® were investigated by UV-visible absorption, fluorescence emission, singlet oxygen emission, and time-resolved fluorescence spectroscopies.

Remarkable kinetic stability of α-thiocarbamoyl substituted 4-methoxybenzylcations

1998 ◽  
Vol 76 (12) ◽  
pp. 1910-1915 ◽  
Author(s):  
Robert A McClelland ◽  
Victoria E Licence ◽  
John P Richard ◽  
Kathleen B Williams ◽  
Shrong-Shi Lin
Keyword(s):  
Key Words ◽  
Strong Interaction ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Visible Absorption ◽  
Methyl Group ◽  
Thioamide Group ◽  
Azide Ion ◽  
Uv Visible ◽  
Leaving Groups

4-Methoxybenzyl cations bearing α-(N,N-dimethylcarbamoyl) and α-(N,N-dimethylthiocarbamoyl) substituents have been generated photochemically upon irradiation of precursors with pentafluorobenzoate or 4-methoxybenzoate leaving groups. The ions have been observed with flash photolysis in 40:60 acetonitrile:water and in 50:50 methanol:water, and rate constants were measured for their decay in solvent alone and for their capture by azide ion. The cations so studied and their lifetimes in 40% acetonitrile are 6, ArC+H-CONMe2, 0.6 μs; 2, ArC+H-CSNMe2, 7 ms; and 4, ArC+(CH3)-CSMe2, 6 ms, where Ar = 4-MeOC6H4. The cation 4 reacts with solvent by elimination of a proton from the α-methyl group, and the rate constant for solvent addition must be less than 1 s-1. The CSNMe2 substituted cations are 105-107-fold longer lived than analogs where the thioamide group has been replaced with an α-methyl. The UV-visible absorption spectra of these two cations also show significant differences from those of typical 4-methoxybenzyl cations. Thus, both the lifetimes and spectra point to a strong interaction of the benzylic centre with the thioamide group. Key words: flash photolysis, thiocarbamoyl stabilized carbocation, photosolvolysis.

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