Nonlinear Optical Molecular Switches for Alkali Ion Identification

Plaquet, Aurélie; Champagne, Benoı̂t; Castet, Frédéric

doi:10.3390/molecules190710574

Cited by 14 publications

(6 citation statements)

References 49 publications

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“…A redox switch linked with internal rotation is reported . The pH switches can alternate between two chemical forms displaying NLO contrast through the proton transfer triggered for organic molecules. − The ion recognition switches can be as selective ion sensors which can be used as a powerful and multiusage detection tool due to interaction between organic complexants and ions. ,− In these switches, the chemical change alters the form (molecular structure) to display NLO contrast.…”

Section: Introductionmentioning

confidence: 99%

An External Electric Field Manipulated Second-Order Nonlinear Optical Switch of an Electride Molecule: A Long-Range Electron Transfer Forms a Lone Excess Electron Pair and Quenches Singlet Diradical

Wang

Zhou

et al. 2016

J. Phys. Chem. C

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An electride molecule e–···K(1)+···calix[4]pyrrole···K(2)+···e– as an external electric field (F) manipulated nonlinear optical (NLO) switch is designed theoretically for the first time. As this molecule is an unusual singlet diradical electride molecule with two easily driven excess electrons (by electric field) at two opposite ends of the molecule, a novel switching mechanism of electronic structure isomerization emerges as a distinctive nonbonding evolution in the electride molecule. A small electric field driving leads to a long-range excess electron transfer from one side K(1) through the middle calix[4]pyrrole to the other side K(2), forms a lone excess electron pair of s-type rather than a single bond, and quenches the singlet diradical. Meanwhile, the molecular electronic structure becomes K(1)+···calix[4]pyrrole···K(2)+···2e–. Therefore, the small electric field driving brings a very high static first hyperpolarizability (β0) contrast from 0 (F = 0, Off form) to 4.060 × 105 au (F = a small nonzero value of 5 × 10–4 au, On form). Notably, under the electric field of 30 × 10–4 au, β0 reaches the largest value of 3.147 × 106 au and the molecule displays the most optimal NLO switching behavior. Furthermore, we consider also that 4H atoms of calix[4]pyrrole are substituted with 4F and 2Be atoms, respectively; then the 2Be and 4F substitution effects on the NLO switch in electride molecules are exhibited. This work opens a new research field of an electric field manipulated NLO switch of electride molecules.

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Section: Introductionmentioning

confidence: 99%

An External Electric Field Manipulated Second-Order Nonlinear Optical Switch of an Electride Molecule: A Long-Range Electron Transfer Forms a Lone Excess Electron Pair and Quenches Singlet Diradical

Wang

Zhou

et al. 2016

J. Phys. Chem. C

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“…The variation of Hyper‐Rayleigh scattering (β HRS ) and the depolarization ratio (DR) shown in Table can be rationalized by complexation and structural evidence . The lowest value of β and DR, and the highest value of β HRS for TUD1‐perchlorate, TUD1‐benzoate and TUD1‐salicylate complexes confirms short bond length between these anions and TUD1 which confirm their strong complexation and higher selectivity . This was ensured by the lowest values of the sum of the four hydrogen bonds for these complexes.…”

Section: Resultsmentioning

confidence: 99%

Carbon‐based Nanosensors for Salicylate Determination in Pharmaceutical Preparations

et al. 2019

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Thiourea derivative‐based carbon paste electrode (TUD1‐CPE) was constructed as a potentiometric sensor for the determination of salicylate anion in pharmaceutical formulations, Aspocid® and Aspirin®. The optimized CPE contained 45.5 % graphite, 0.5 % reduced graphene oxide (rGO), 46.0 % nitrophenyl octyl ether (NPOE) plasticizer, 5.0 % TUD1 ionophore, and 3.0 % tridodecylmethyl ammonium chloride as additive. The incorporation of NPOE of high dielectric constant, and rGO in electrode caused better performance of the sensor; Nernstian response of 59.0 mV decade−1 in the concentration range of 10−1–10−5 mole L−1, a detection limit of 1×10−5 mole L−1 in a very short response time of 6 seconds. The prepared sensor showed high selectivity against similar anions (i. e. ClO4- , benzoate, I−, SCN−). Selectivity was confirmed by calculating the formation constant (Kβ) using sandwich membrane method, where Kβ for TUD1‐salicylate is 100.43. Theoretical calculations at DFT‐B3LY/6‐31G** level of theory were performed to find interaction mechanism, Energies of HOMO and LUMO orbitals, non‐linear optical (NLO) properties (the electronic dipole moment (μ), first‐order hyperpolarizability (β), the hyper‐Rayleigh scattering (βHRS) and the depolarization ratio (DR)), and other global properties; these calculations showed lower values of β and DR, higher value of βHRS, and the shortest lengths of the four N−H bonds between TUD1 and salicylate which confirm their strong complexation and salicylate‐selectivity. Also, all the studied anion‐TUD1 exhibited relatively high NLO properties, and these results were considered as a preliminary study for investigating new types of NLO bearing materials. The sensors were applied successfully for the determination of salicylate anion in Aspocid® and Aspirin®.

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“…Recently, Champagne's group and two Chinese groups demonstrated that second-order nonlinear optical (NLO) molecular switches can be used as selective cation sensors by means of ab initio calculations, providing a powerful detection tool complementary to standard techniques based on variations in the absorption or fluorescence spectra. [27][28][29][30] As we know, the second-order NLO signal is restricted to the requirement of a noncentrosymmetric conformation, [31][32][33] whereas third-order susceptibility χ (3) is a fourth-order tensor without limitation of the symmetry center, which means theoretically all materials possess third-order NLO effects. As one kind of third-order nonlinear absorption effect, two-photon absorption in a metal-dependent manner has attracted much attention in the past decade.…”

Section: Introductionmentioning

confidence: 99%

Macrocyclic Se₄N₂[7,7]ferrocenophane and Se₂N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties

Song

et al. 2016

Dalton Trans.

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Two novel macrocyclic polyselena[n]ferrocenophanes containing a pendent benzyl unit, 20-membered Se4N2[7,7]ferrocenophane (L1) and 10-membered Se2N[10]ferrocenophane (L2), were designed and synthesized. The reaction of L1 with two molar amounts of metal salts (M = Cu(+), Cu(2+), Pd(2+) and Hg(2+)) led to six dimetallic complexes 1-6. A crystallographic study revealed that each metal center in 1-5 was tetracoordinated to two selenium atoms from different ferrocene units, one aliphatic nitrogen atom and one co-ligand. The structures of the complexes contain a two-fold axis perpendicular to the molecular plane with two pendant benzyl moieties in an anti-conformation. Macrocycle L1 gives significant electrochemical, linear and third-order nonlinear optical responses to Cu(2+) and Hg(2+). The DFT/B3LYP calculations of 4 demonstrated a small HOMO-LUMO energy gap and delocalization of the π-electron cloud in the frontier molecular orbitals, which led to the enhancement of molecular NLO properties after complexation. The results show that the oxidation state of the ferrocene unit is accompanied by significant differences in the corresponding absorption spectra and third-order NLO properties.

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Nonlinear Optical Molecular Switches for Alkali Ion Identification

Cited by 14 publications

References 49 publications

An External Electric Field Manipulated Second-Order Nonlinear Optical Switch of an Electride Molecule: A Long-Range Electron Transfer Forms a Lone Excess Electron Pair and Quenches Singlet Diradical

An External Electric Field Manipulated Second-Order Nonlinear Optical Switch of an Electride Molecule: A Long-Range Electron Transfer Forms a Lone Excess Electron Pair and Quenches Singlet Diradical

Carbon‐based Nanosensors for Salicylate Determination in Pharmaceutical Preparations

Macrocyclic Se₄N₂[7,7]ferrocenophane and Se₂N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties

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Nonlinear Optical Molecular Switches for Alkali Ion Identification

Cited by 14 publications

References 49 publications

An External Electric Field Manipulated Second-Order Nonlinear Optical Switch of an Electride Molecule: A Long-Range Electron Transfer Forms a Lone Excess Electron Pair and Quenches Singlet Diradical

An External Electric Field Manipulated Second-Order Nonlinear Optical Switch of an Electride Molecule: A Long-Range Electron Transfer Forms a Lone Excess Electron Pair and Quenches Singlet Diradical

Carbon‐based Nanosensors for Salicylate Determination in Pharmaceutical Preparations

Macrocyclic Se4N2[7,7]ferrocenophane and Se2N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties

Contact Info

Product

Resources

About

Macrocyclic Se₄N₂[7,7]ferrocenophane and Se₂N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties