Syntheses of four new pyridinium phenolates with caged phenolate functionalities as chromophores for quadratic optics

Ay, Emel; Chaumeil, Hélène; Barsella, Alberto

doi:10.1016/j.tet.2011.10.115

Cited by 7 publications

(10 citation statements)

References 19 publications

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“…These movements seem rapid enough to effectively protect the phenolate function. Eventually, EFISHG experiments have been readily performed on compounds 1b-d. 13 These results corroborate the above hypothesis and also indicate that a phenolate function is little bulky enough to allow, in the particular case of 1b, the swing of a chain of ten atoms.…”

Section: Discussionsupporting

confidence: 83%

“…[4][5][6][7][8][9][10][11][12] In this context, we have recently synthesised pyridinium phenolates bearing saturated handles of various lengths (compounds 1a-d, Scheme 1). 13 A moderate twist angle was introduced by anchoring two methyl groups at the meta position of the pyridine ring to retain reasonable NLO responses. No aggregate formation has been demonstrated at concentration of between 10 À2 and 10 À4 M and that EFISHG experiments have been readily performed on compounds 1b-d. 13 However, before considering any application of these derivatives, it seemed us essential to understand the dynamic behaviour of the introduced handles.…”

Section: Introductionmentioning

confidence: 99%

“…13 A moderate twist angle was introduced by anchoring two methyl groups at the meta position of the pyridine ring to retain reasonable NLO responses. No aggregate formation has been demonstrated at concentration of between 10 À2 and 10 À4 M and that EFISHG experiments have been readily performed on compounds 1b-d. 13 However, before considering any application of these derivatives, it seemed us essential to understand the dynamic behaviour of the introduced handles.The molecular structure of compounds 1a-d undergoes two structural movements: a twist H, around the CAC intercyclic bond and an alkyl chain swing U. Variable-temperature 1 H NMR (dynamic NMR or D NMR) is a method of choice to study these processes. Unfortunately, 1a-d are too poorly soluble in the commonly used NMR solvents.…”

mentioning

confidence: 99%

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Concerning restricted rotations in pyridinyl anisoles and pyridinyl phenols bearing saturated handles, and their solid state structures

Nouën

Chaumeil

et al. 2014

Tetrahedron Letters

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Section: Discussionsupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Concerning restricted rotations in pyridinyl anisoles and pyridinyl phenols bearing saturated handles, and their solid state structures

Nouën

Chaumeil

et al. 2014

Tetrahedron Letters

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“…13c, 17 Successful synthesis was established by 1 H NMR and ESI-MS. Tb-DO3A (1,4,7,10-tetraazacyclododecane-1,4,7-tris(acetic acid)) and Tb-DO2A (1,4,7,10-tetraazacyclododecane-1,7-bis(acetic acid)) were synthesized according to literature precedent for lanthanide carboxylate complexes. 17b, 18 The tert-butyl protected DO3A and DO2A are commercially available (Macrocyclics).…”

Section: Methodsmentioning

confidence: 99%

Basis for Sensitive and Selective Time-Delayed Luminescence Detection of Hydroxyl Radical by Lanthanide Complexes

et al. 2013

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Molecular probes for the detection of hydroxyl radical (HO•) by time-delayed luminescence spectroscopy directly in water at neutral pH with high sensitivity and selectivity are presented. The bimolecular probes consist of a lanthanide complex with open coordination sites and a reactive pre-antenna composed of an aromatic acid or amide; the latter binds to and sensitizes terbium emission upon hydroxylation by HO•. These probes exhibit long luminescence lifetimes compatible with time-delayed measurements that remove interfering background fluorescence from the sample. Six different reactive pre-antenna (benzoate, benzamide, isophthalate, isophthalamide, trimesate, and trimesamide) and two different terbium complexes (Tb-DO3A and Tb-DO2A) were evaluated. Of these the trimesamide/Tb-DO3A system enables the most sensitive detection of HO• with a ca. 1000-fold increase in metal-centered time-delayed emission upon hydroxylation of the pre-antenna to 2-hydroxytrimesamide. Excellent selectivity for both the trimesamide/Tb-DO3A and trimesate/Tb-DO3A systems over other reactive oxygen and nitrogen species are observed. Notably, the increase in metal-centered luminescence intensity is not associated with a decrease in the hydration number (q) of Tb-DO3A, suggesting that the antenna is interacting with the lanthanide via a second sphere coordination environment or that coordination by the antenna occurs by displacement of one or more of the carboxylate arms of DO3A. Formation of a weak ternary complex Tb-DO3A•hydroxytrimesamide was confirmed by temperature-dependent titration and a decrease in Kapp with increasing temperature.

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“…Many research groups have studied other probes inspired by the molecular structure of compound 1 . In general, the solvatochromic dyes exhibiting a pronounced negative solvatochromism have a pyridinium group as the electron acceptor and a phenolate as the electron‐donor group . Recently, our group studied the solvatochromism of nitro‐substituted benzylideneaminophenolates, which have phenolate donor groups and 4‐nitro or 2,4‐dinitrophenyl acceptor groups connected through a CN conjugated bridge.…”

Section: Introductionmentioning

confidence: 99%

Solvatochromic behavior of dyes with dimethylamino electron-donor and nitro electron-acceptor groups in their molecular structure

Melo

Nandi

Domínguez

et al. 2014

J. Phys. Org. Chem.

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Six dyes with N,N‐dimethylaminophenyl and 4‐nitrophenyl or 2,4‐dinitrophenyl groups in their molecular structures were prepared and characterized. These compounds have different conjugated bridges (CC, CN, and NN) connecting the electron‐donor and the electron‐acceptor groups. All compounds are solvatochromic, with reverse solvatochromism occurring. The solvatochromic band observed in each spectrum for the dyes is due to a π ➔ π* transition, of an intramolecular charge transfer nature, which occurs from the electron‐donor N,N‐dimethylaminophenyl group to the electron‐acceptor group in the molecules, which is reinforced by the structures of the compounds optimized by applying density functional theory, which exhibit high planarity. The reverse solvatochromism was explained considering two resonance structures. The benzenoid form is better stabilized in less polar solvents and characterizes the region displaying positive solvatochromism, while the dipolar form is better stabilized in more polar solvents, in the region of negative solvatochromism. The Catalán multiparametric approach was used to study the contribution of solvent acidity, basicity, dipolarity, and polarizability to the solvatochromism exhibited by the compounds. These compounds are good candidates for the investigation of the polarizability and, to a lesser extent, the dipolarity of the medium, with very little interference from specific interactions of the solvent through hydrogen bonding. Copyright © 2014 John Wiley & Sons, Ltd.

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Syntheses of four new pyridinium phenolates with caged phenolate functionalities as chromophores for quadratic optics

Cited by 7 publications

References 19 publications

Concerning restricted rotations in pyridinyl anisoles and pyridinyl phenols bearing saturated handles, and their solid state structures

Concerning restricted rotations in pyridinyl anisoles and pyridinyl phenols bearing saturated handles, and their solid state structures

Basis for Sensitive and Selective Time-Delayed Luminescence Detection of Hydroxyl Radical by Lanthanide Complexes

Solvatochromic behavior of dyes with dimethylamino electron-donor and nitro electron-acceptor groups in their molecular structure

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