New tetrazines substituted by heteroatoms including the first tetrazine based cyclophane: Synthesis and electrochemical properties

Gong, Yong-Hua; Audebert, Pierre; Tang, Jie; Miomandre, Fabien; Clavier, Gilles; Badré, Sophie; Méallet‐Renault, Rachel; Marrot, Jérôme

doi:10.1016/j.jelechem.2006.05.014

Cited by 46 publications

(48 citation statements)

References 11 publications

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“…The decrease of λ i is closely related to the change in the shape of the LUMO, which becomes completely delocalized for (ArCC) 2 Tz (see Figure 1 for (PhCC) 2 Tz). In addition, we have observed a cross correlation between the shapes of the LUMO and LUMO + 1 orbitals for Ph 2 Tz and (PhCC) 2 Tz. Similar correlation is also observed for the HOMO and HOMO-1 orbitals (see Figure 1).…”

Section: Resultsmentioning

confidence: 75%

“…Tetrazine derivatives represent the most electron-deficient aromatic family [1][2][3] and exhibit interesting semiconducting and opto-electronic properties such as redox reversibility on reduction at low potentials [2][3][4]5 and a characteristic n → π* low energy transition, [5][6][7][8] which can be exploited in the fabrication of OLEDs, 9 OFETs, 10 and solar cells. 11,12 N-type semiconducting properties have been profusely studied either for 3,6-diphenyl-s-tetrazine (Ph 2 Tz, see Chart 1) and other diaryl-s-tetrazines (Ar 2 Tz).…”

Section: Introductionmentioning

confidence: 99%

“…Actually for some Ar 2 Tz halogenated derivatives, the calculated electronic coupling values appear to be of the same order of magnitude than those reported before for the best naphthalene diimide 19 and perylene n-type semiconductors, 20,21 which have been successfully used in electronic devices. [22][23][24][25][26] Nevertheless, the high values of internal reorganization energy (λ i ) predicted for those Ar 2 Tz derivatives might preclude their use as reliable semiconducting materials. 17 The increase in the delocalization of the LUMO orbital could be achieved by the introduction of ethynylene groups (-C≡C-) as a bridge between the three aromatic rings; in fact the ethynylene group, due to its axial symmetry, could allow to extend the conjugation to adjacent arylene groups.…”

mentioning

confidence: 99%

“…17 The increase in the delocalization of the LUMO orbital could be achieved by the introduction of ethynylene groups (-C≡C-) as a bridge between the three aromatic rings; in fact the ethynylene group, due to its axial symmetry, could allow to extend the conjugation to adjacent arylene groups. [27][28][29][30][31][32] Note also that the actual synthesis of s-tetrazine ethynylene derivatives is possible through cross-coupling reactions on some s-tetrazine compounds (compounds a and b in Chart 1), as shown by Novák and Kotschy, 33 though we are not aware of any attempt for (ArCC) 2 Tz compounds.…”

mentioning

confidence: 99%

“…For those reasons, we aim thereby to explore the electronic properties of this new family of potential n-type semiconducting compounds based on bis(aryleneethynylene)-s-tetrazine structures, (ArCC) 2 Tz (see also Chart 1). …”

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confidence: 99%

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Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

et al. 2015

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We theoretically describe in this work the n-type semiconducting behavior of a set of bis(arylene-ethynylene)-s-tetrazines ((ArCC) 2 Tz), by comparing their electronic properties with those of their parent diaryl-s-tetrazines (Ar 2 Tz) after the introduction of ethynylene bridges. The significantly reduced internal reorganization energy for electron transfer is ascribed to an extended delocalization of the LUMO for (ArCC) 2 Tz as opposite to that for Ar 2 Tz, which was described mostly localized on the s-tetrazine ring. The largest electronic coupling and the corresponding electron transfer rates found 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 for bis(phenyl-ethynylene)-s-tetrazine, as well as for some halogenated derivatives, are comparable to those reported for the best performing n-type organic semiconductors materials such as diimides and perylenes. The theoretical mobilities for the studied compounds turn out to be in the range 0.3 -1.3 cm 2 V −1 s −1 , close to values experimentally determined for common n-type organic semiconductors used in real devices. In addition, ohmic contacts can be expected when these compounds are coupled to metallic cathodes such as Na, Ca and Sm. For these reasons, the future application of semiconducting bis(phenyl-ethynylene)-s-tetrazine and its fluorinated and brominated derivatives in optoelectronic devices is envisioned.

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Section: Resultsmentioning

confidence: 75%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

et al. 2015

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Site‐Specific Dual Labeling of Proteins on Cysteine Residues with Chlorotetrazines

et al. 2018

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Dual-labeled biomolecules constitute a new generation of bioconjugates with promising applications in therapy and diagnosis. Unfortunately, the development of these new families of biologics is hampered by the technical difficulties associated with their construction. In particular, the site-specificity of the conjugation is critical as the number and position of payloads can have a dramatic impact on the pharmacokinetic of the bioconjugate. Here, we introduce dichlorotetrazine as a trivalent platform for the selective double-modification of proteins on cysteine residues. This strategy is applied to the dual-labeling of albumin with a macrocyclic chelator for nuclear imaging and a fluorescent probe for fluorescence imaging.

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Dynamic Nucleophilic Aromatic Substitution of Tetrazines

et al. 2021

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A dynamic nucleophilic aromatic substitution of tetrazines (SNTz) is presented herein. It combines all the advantages of dynamic covalent chemistry with the versatility of the tetrazine moiety. Indeed, libraries of compounds or sophisticated molecular structures can be easily obtained, which are susceptible to post‐functionalization by inverse electron demand Diels–Alder (IEDDA) reaction, which also locks the exchange. Additionally, the structures obtained can be disassembled upon the application of the right stimulus, either UV irradiation or a suitable chemical reagent. Moreover, SNTz is compatible with the imine chemistry of anilines. The high potential of this methodology has been proved by building two responsive supramolecular systems: A macrocycle that displays a light‐induced release of acetylcholine; and a truncated [4+6] tetrahedral shape‐persistent fluorescent cage, which is disassembled by thiols unless it is post‐stabilized by IEDDA.

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New tetrazines substituted by heteroatoms including the first tetrazine based cyclophane: Synthesis and electrochemical properties

Cited by 46 publications

References 11 publications

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

Site‐Specific Dual Labeling of Proteins on Cysteine Residues with Chlorotetrazines

Dynamic Nucleophilic Aromatic Substitution of Tetrazines

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