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Fused ring effect on optical nonlinearity and structure property relationship of anthracenyl chalcone based push-pull chromophores.

ABSTRACT: The Ultraviolet-visible (UV-Vis) spectra indicate that anthracenyl chalcones (ACs) have high maximum wavelengths and good transparency windows for optical applications and are suitable for optoelectronic applications owing to their HOMO-LUMO energy gaps (2.93 and 2.76 eV). Different donor substituents on the AC affect their dipole moments and nonlinear optical (NLO) responses. The positive, negative, and neutral electrostatic potential regions of the molecules were identified using molecular electrostatic potential (MEP). The stability of the molecule on account of hyperconjugative interactions and accompanying charge delocalization was analyzed using natural bond orbital (NBO) analysis. Open and closed aperture Z-scans were performed using a continuous-wave frequency-doubled diode-pumped solid-state (DPSS) laser to measure the nonlinear absorption and nonlinear refractive index coefficients, respectively. The valley-to-peak profile of AC indicated a negative nonlinear refractive index coefficient. The obtained single crystals possess reverse saturation absorption due to excited-state absorption. The structural and nonlinear optical properties of the molecules have been discussed, along with the role of anthracene substitution for enhancing the nonlinear optical properties. The calculated third-order susceptibility value was 1.10 x10-4 esu at an intensity of 4.1 kW/cm2, higher than the reported values for related chalcone derivatives. The NLO response for both ACs offers excellent potential in optical switching and limiting applications.

SUBMITTER: Zainuri DA

PROVIDER: S-EPMC8478194 | biostudies-literature |

REPOSITORIES: biostudies-literature

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

Project description: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.

| S-EPMC6515425 | biostudies-literature

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Project description:In this study, two different classes of push-pull chromophores were synthesized in modest to excellent yields by formal [2+2] cycloaddition-retroelectrocyclization (CA-RE) reactions. N-Methyl indole was introduced as a new donor group to activate alkynes in the CA-RE transformations. Depending on the side groups' size and donor/acceptor characteristics, N-methyl indole-containing compounds exhibited λmax values ranging between 378 and 658 nm. The optoelectronic properties of the reported D-A-type structures were studied by UV/vis spectroscopy and computational studies. The complete regioselectivity observed in the products was elaborated by one-dimensional (1D) and two-dimensional (2D) NMR studies, and the electron donor strength order of N-alkyl indole and triazene donor groups was also established. The intramolecular charge-transfer characteristics of the target push-pull chromophores were investigated by frontier orbital depictions, electrostatic potential maps, and time-dependent density functional theory calculations. Overall, the computational and experimental results match each other. Integrating a new donor group, N-alkyl indole, into the substrates used in formal [2+2] cycloaddition-retroelectrocyclizations has significant potential to overcome the limited donor-substituted substrate scope problem of CA-RE reactions.

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Synthesis and Nonlinear Optical Behavior of Thermally Stable Chromophores Based on 9,9-Dimethyl-9<i>H</i>-fluoren-2-amine: Improving Intrinsic Hyperpolarizability through Modulation of "Push-Pull".

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Synthesis of novel cyclosiloxane monomers containing push-pull moieties and their anionic ring opening polymerization.

Project description:The synthesis of three novel tetracyclosiloxane monomers modified either with a nitroaniline (NA) or with a Disperse Red 1 (DR1) push-pull group and their ring opening polymerization reaction in the presence of tetramethylammonium hydroxide are presented. The prepared monomers and polymers were characterized by different spectral methods and gel permeation chromatography. For the crystalline monomers, the structures were further proven by single crystal X-ray diffraction. Dynamic scanning calorimetry shows that the polymers that carry NA groups have a glass transition temperature (T g) well below room temperature (RT), while the one that carries DR1 groups melts at 55 °C. The transition temperatures have a strong effect on permittivity as indicated by broadband impedance spectroscopy measurements conducted at different temperatures and frequencies. The polymers modified with NA groups have a high permittivity (maximum value of 17.3) at RT, suggesting the polar groups to be mobile and orientation polarization to be effective. However, the polar groups of the polymer modified with DR1 are frozen and thus cannot contribute to the permittivity via orientation polarization. Consequently, the permittivity is only 8.8 at RT, but increases to 22 above the melting temperature, where the dipoles are mobile. Because of the high dielectric permittivity and rather low T g, the polymers modified with NA are attractive as active dielectric materials in actuators, capacitors, and stretchable electronics, whereas the polymer modified with DR1 may be of interest in nonlinear optical devices.

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| S-EPMC3562390 | biostudies-literature

Anion-enhanced excited state charge separation in a spiro-locked N-heterocycle-fused push-pull zinc porphyrin.

Project description:A new type of push-pull charge transfer complex, viz., a spiro-locked N-heterocycle-fused zinc porphyrin, ZnP-SQ, is shown to undergo excited state charge separation, which is enhanced by axial F- binding to the Zn center. In this push-pull design, the spiro-quinone group acts as a 'lock' promoting charge transfer interactions by constraining mutual coplanarity of the meso-phenol-substituted electron-rich Zn(ii) porphyrin and an electron deficient N-heterocycle, as revealed by electrochemical and computational studies. Spectroelectrochemical studies have been used to identify the spectra of charge separated states, and charge separation upon photoexcitation of ZnP has been unequivocally established by using transient absorption spectroscopic techniques covering wide spatial and temporal regions. Further, global target analysis of the transient data using GloTarAn software is used to obtain the lifetimes of different photochemical events and reveal that fluoride anion complexation stabilizes the charge separated state to an appreciable extent.

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A push-pull unsymmetrical subphthalocyanine dimer.

Project description:Unsymmetrical subphthalocyanine fused dimers have been prepared from appropriate ortho-dinitrile SubPc precursors. In particular, either electron-donating or electron-accepting substituents have been introduced on each SubPc constituent unit, resulting in unprecedented push-pull ?-extended curved aromatic macrocycles. From fluorescence experiments in solvents of different polarity we conclude a dual fluorescence, namely a delocalized singlet excited state (1.73 eV) and a polarized charge transfer state (<1.7 eV). Pump probe experiments corroborate the dual nature of the fluorescence. On one hand, the delocalized singlet excited state gives rise to a several nanosecond lasting intersystem crossing yielding the corresponding triplet excited state. On the other hand, the polarized charge transfer state deactivates within a few picosesonds. Visualization of the charge transfer state was accomplished by means of molecular modeling with a slight polarization of the HOMO towards the electron donor and of the LUMO towards the electron acceptor.

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Experimental and Theoretical Insights into the Optical Properties and Intermolecular Interactions in Push-Pull Bromide Salts.

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| S-EPMC6470380 | biostudies-literature

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