s-Tetrazines functionalized with phenols: synthesis and physico-chemical properties

Jullien-Macchi, Eva; Alain-Rizzo, Valérie; Allain, Clémence; Dumas‐Verdes, Cécile; Audebert, Pierre

doi:10.1039/c4ra03831b

Cited by 18 publications

(12 citation statements)

References 31 publications

(25 reference statements)

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“…In these compounds, electronic excited state energy is dissipated slowly both through light emission and through intramolecular vibrational relaxation to eventually dissipate as heat. Note that the DNP–Tz–Cl studied here exhibits reasonable fluorescence and long excited state lifetime, while 4-nitrophenoxychlorotetrazine did not appear to be stable in the series of related compounds reported by the Audebert group …”

Section: Discussionmentioning

confidence: 63%

“…Note that the DNP−Tz−Cl studied here exhibits reasonable fluorescence and long excited state lifetime, while 4-nitrophenoxychlorotetrazine did not appear to be stable in the series of related compounds reported by the Audebert group. 43 Effect of structure. Across the X−Tz−Cl series, QY PC increases as X = DNP, DNAZ, P at 532 nm and DNP, P, DNAZ at 355 nm, but with a small total variation ranging from 0.0015 to 0.006.…”

Section: ■ Discussionmentioning

confidence: 99%

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Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

et al. 2016

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High explosives that are photoactive, i.e., can be initiated with light, offer significant advantages in reduced potential for accidental electrical initiation. We examined a series of structurally related tetrazine based photoactive high explosive materials to detail their photochemical and photophysical properties. Using photobleaching infrared absorption, we determined quantum yields of photochemistry for nanosecond pulsed excitation at 355 and 532 nm. Changes in mass spectrometry during laser irradiation in vacuum measured the evolution of gaseous products. Fluorescence spectra, quantum yields, and lifetimes were measured to observe radiative channels of energy decay that compete with photochemistry. For the 6 materials studied, quantum yields of photochemistry ranged from <10(-5) to 0.03 and quantum yield of fluorescence ranged from <10(-3) to 0.33. In all cases, the photoexcitation nonradiatively relaxed primarily to heat, appropriate for supporting photothermal initiation processes. The photochemistry observed was dominated by ring scission of the tetrazine, but there was evidence of more extensive multistep reactions as well.

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Section: Discussionmentioning

confidence: 63%

Section: ■ Discussionmentioning

confidence: 99%

Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

et al. 2016

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“…Concerning the modification of substituents at the carbons C(3)/C(6) after tetrazine ring formation, the availability of 3,6-dichloro-s-tetrazine [92] constituted a true landmark in the field owing to the great potential of this compound to generate a vast diversity of substitution patterns, both symmetrical and unsymmetrical, by aromatic nucleophilic substitution of the chlorine atoms [93][94][95], as well as by other ways such as Pd-catalyzed C-C coupling reactions [96][97]. Other advances, of particular interest in the field of energetic and explosive materials, are the new procedures introduced to prepare mono-and bi-N-oxides of the s-tetrazine nucleus [98][99].…”

Section: Synthesis Of S-tetrazine Derivativesmentioning

confidence: 99%

“…According to molecular calculations [97,[101][102][103][104], this is a general feature of s-tetrazine derivatives, regardless of the substituents connected to C(3) and/or C(6) (unsaturated and aromatic included), though the nature of the substituents obviously influences the orbital energy. The electron transitions n  π*(LUMO) that take place by absorption of light of wavelength around 530 nm, with low molar adsorptivities (typically, ε ≈ 600 L⋅mol −1 ⋅cm −1 ) [81,94,97] due to symmetry mismatch between the orbital involved, are responsible for the characteristic colour (red-pink-purple) of the s-tetrazine derivatives.…”

Section: General Perspective On the Properties And Applications S-tetrazinesmentioning

confidence: 99%

Anion-π and lone pair-π interactions with s-tetrazine-based ligands

Savastano

García-Gallarín

Torre

et al. 2019

Coordination Chemistry Reviews

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Most of traditional and contemporary interest in s-tetrazine derivatives focuses onto their redox properties, reactivity and energy density. In recent times, however, an increasing number of reports highlighted the possible usefulness of the s-tetrazine moiety as a binding site for anionic and electron rich species, according to the high and positive quadrupolar moment of this heterocycle and the consequent strength of anion-π and lone pair-π interactions. Herein, after giving a quick perspective on s-tetrazine properties and on how they foster these types of π interactions, we present statistical and critical examination of the available structural data, doing justice to the debated topic of the existence and directionality of anion-and lone pair-π interactions. Finally, available literature material concerning the usage of s-tetrazine as supramolecular binding site in solution, i.e. paving the way to applications such as molecular recognition and sensing, is presented and discussed. Contents 1. Introduction 2. s-Tetrazine Synthesis & Properties 2.1. Synthesis of s-tetrazine derivatives 2.2. General perspective on the properties and applications s-tetrazines 2.3. Anion-π and lone pair-π: nature of the interactions and relevance of the s-tetrazine ring 3. Anion-π and lone pair-π interactions with s-tetrazines in the solid-state: CSD Survey 3.1. Methodology and rationale of the survey 3.2. Structural data analysis 4. Selected evidences of anion-π and lone pair-π interactions with s-tetrazines in the solid state 5. Anion-π and lone pair-π interactions with s-tetrazines in solution 6. Conclusions Appendix A. Supplementary data Referencesthe aromatic s-tetrazine ring enables compact molecular packings which are essential to realize substances with a high (volumetric) energy density [116,117]. This is a field that continues very active in seeking for new s-tetrazine derivatives of interest [118][119][120].Other important applications of s-tetrazines derive from their particular reactivity, that serves as the base of the usefulness that these structures are proving in molecular biology studies, as reacting partners in bioorthogonal chemistry [121] methods (a field that has boosted the research and literature devoted to stetrazines from the first 2000s) [84,122]. These applications take advantage of two properties of stetrazines: i) the propensity of the s-tetrazine nucleus to act as 2,3-diazadiene in fast inverse-electrondemand Diels-Alder (iedDA) reactions with alkenes and alkynes that affords, in a first term, a bicyclic adduct which immediately suffers a retro-Diels-Alder (rDA) reaction, evolving N 2 , to give rise to dihydropyridazines or aromatic pyridazines, respectively (Scheme 2) [123,124]; ii) the inertness of s-tetrazine derivatives towards natural substances under biological conditions. Scheme 2 to be inserted about here.But the property that focused our interest in s-tetrazines, and constitutes the main subject of this review, is their ability to establish non-covalent bonds to negatively charged species (a...

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“…13 In addition we have chosen a link composed of 3 or 4 atoms (C and O atoms) instead of a unique oxygen atom because the phenoxytetrazine derivatives are not highly uorescent. 17,18…”

Section: Introductionmentioning

confidence: 99%

Original electroactive and fluorescent bichromophores based on non-conjugated tetrazine and triphenylamine derivatives: towards more efficient fluorescent switches

et al. 2015

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s-Tetrazines functionalized with phenols: synthesis and physico-chemical properties

Abstract: International audienc

Cited by 18 publications

References 31 publications

Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

Anion-π and lone pair-π interactions with s-tetrazine-based ligands

Original electroactive and fluorescent bichromophores based on non-conjugated tetrazine and triphenylamine derivatives: towards more efficient fluorescent switches

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