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Tetrazines: A World of New Molecules Emerging from Old Chemistry
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Tetrazines: A World of New Molecules Emerging from Old Chemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (28 February 2021) | Viewed by 29231

Special Issue Editors

Prof. Dr. Pierre Audebert

E-Mail Website
Guest Editor
1. PPSM, Av. Des Sciences, 91100 Gif s. Yvette, CNRS UMR 8531, 61, Avenue du Président Wilson, CEDEX, 94235 Cachan, France
2. XLIM, UMR CNRS 7252 123, Avenue Albert Thomas, CEDEX, 87060 Limoges, France
Interests: organic heterocyclic chemistry (polyazaaromatics); tetrazines; electrochemistry; NLO; sol–gel chemistry; nanomaterials; fluorescence; perovskites
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Jean-Cyrille Hierso

E-Mail Website
Guest Editor
Université de Bourgogne Franche-Comté, Dijon, France; IUF honorary member
Interests: organometallic chemistry; ligand design; homo- and heterogeneous catalysis; chemical physics; materials science Achievements and Distinctions: In 2011, awarded the National Prize for Coordination Chemistry from the French Chemical Society (SCF), the EurJIC-Young Investigator Award 2012, and at the end of 2012 he was elected a junior Member of the French Academy “Institut Universitaire de France” (IUF)

Special Issue Information

Dear Colleagues,

Research into the chemistry of tetrazines has been soaring since the beginning of this century,  mainly due to two major discoveries. The first is the “bio click” chemistry, which essentially qualifies as a new type of inverse demand Diels–Alder reaction which is extremely specific and tolerant and, in particular, compatible with biological conditions (hence the name). The second is the tetrazine fluorescence, which is very specific, and has given birth to several specific and original applications. However, even besides these major fields, the field of tetrazine chemistry is gaining popularity, driven by the steadily increasing relative growth of heterocyclic chemistry in comparison with other research fields. For the Special Issue “Tetrazines: A World of New Molecules Emerging from Old Chemistry”, papers devoted to all fields of tetrazine chemistry will be welcome, with an emphasis on original contributions on modern click chemistry, and detailing outstanding optical properties like fluorescence and electrofluorochromism. Review articles are also welcome. A classical blind review process will be applied to all submitted contributions.

Professor Pierre Audebert
Professor Jean-Cyrille Hierso
Guest Editors

Keywords

  • tetrazines—click chemistry
  • fluorescence
  • electrofluorochromism catalysis

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Published Papers (7 papers)

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Research

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16 pages, 9798 KiB  
Article
Fluorescent Liquid Tetrazines
by Maximilian Paradiz Dominguez, Begüm Demirkurt, Marion Grzelka, Daniel Bonn, Laurent Galmiche, Pierre Audebert and Albert M. Brouwer
Molecules 2021, 26(19), 6047; https://doi.org/10.3390/molecules26196047 - 6 Oct 2021
Cited by 4 | Viewed by 2797
Abstract
Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as [...] Read more.
Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm−1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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19 pages, 6914 KiB  
Article
Coordination Chemistry of a Bis(Tetrazine) Tweezer: A Case of Host-Guest Behavior with Silver Salts
by Clève D. Mboyi, Ons Amamou, Paul Fleurat-Lessard, Julien Roger, Hélène Cattey, Charles H. Devillers, Michel Meyer, Taoufik Boubaker and Jean-Cyrille Hierso
Molecules 2021, 26(9), 2705; https://doi.org/10.3390/molecules26092705 - 5 May 2021
Viewed by 2786
Abstract
The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing [...] Read more.
The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)-silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6−, BF4−, SbF6−, ClO4−, NTf2−, and OTf−. These compounds were characterized in the solid state by single-crystal X-ray diffraction (XRD) and diffuse reflectance spectroscopy, and in solution by 1H-NMR, mass spectrometry, electroanalysis, and UV-visible absorption spectrophotometry. The X-ray crystal structure of complexes {[Ag(3)][PF6]}∞ (4) and {[Ag(3)][SbF6]}∞ (6), where 3 is 3,3′-[(1,1′-biphenyl)-2,2′-diyl]-6,6′-bis(phenyl)-1,2,4,5-tetrazine, revealed the formation of 1D polymeric chains, characterized by an evolution to a large opening of the original tweezer and a coordination of silver(I) via two chelating nitrogen atom and some C=C π-interactions. Electrochemical and UV spectroscopic properties of the original tweezer and of the corresponding silver complexes are reported and compared. 1H-NMR titrations with AgNTf2 allowed the determination of the stoichiometry and apparent stability of two solution species, namely [Ag(3)]+ and [Ag(3)2]2+, that formed in CDCl3/CD3OD 2:1 v/v mixtures. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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13 pages, 2615 KiB  
Article
Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand
by Oleh Stetsiuk, Abdelkrim El-Ghayoury, Francesc Lloret, Miguel Julve and Narcis Avarvari
Molecules 2021, 26(8), 2122; https://doi.org/10.3390/molecules26082122 - 7 Apr 2021
Cited by 2 | Viewed by 2459
Abstract
Four new compounds of formulas [Cu(hfac)2(L)] (1), [Ni(hfac)2(L)] (2), [{Cu(hfac)2}2(µ-L)]·2CH3OH (3) and [{Ni(hfac)2}2(µ-L)]·2CH3CN (4) [Hhfac = hexafluoroacetylacetone and L [...] Read more.
Four new compounds of formulas [Cu(hfac)2(L)] (1), [Ni(hfac)2(L)] (2), [{Cu(hfac)2}2(µ-L)]·2CH3OH (3) and [{Ni(hfac)2}2(µ-L)]·2CH3CN (4) [Hhfac = hexafluoroacetylacetone and L = 3,6-bis(picolylamino)-1,2,4,5-tetrazine] have been prepared and their structures determined by X-ray diffraction on single crystals. Compounds 1 and 2 are isostructural mononuclear complexes where the metal ions [copper(II) (1) and nickel(II) (2)] are six-coordinated in distorted octahedral MN2O4 surroundings which are built by two bidentate hfac ligands plus another bidentate L molecule. This last ligand coordinates to the metal ions through the nitrogen atoms of the picolylamine fragment. Compounds 3 and 4 are centrosymmetric homodinuclear compounds where two bidentate hfac units are the bidentate capping ligands at each metal center and a bis-bidentate L molecule acts as a bridge. The values of the intramolecular metal···metal separation are 7.97 (3) and 7.82 Å (4). Static (dc) magnetic susceptibility measurements were carried out for polycrystalline samples 1–4 in the temperature range 1.9–300 K. Curie law behaviors were observed for 1 and 2, the downturn of χMT in the low temperature region for 2 being due to the zero-field splitting of the nickel(II) ion. Very weak [J = −0.247(2) cm−1] and relatively weak intramolecular antiferromagnetic interactions [J = −4.86(2) cm−1] occurred in 3 and 4, respectively (the spin Hamiltonian being defined as H = −JS1·S2). Simple symmetry considerations about the overlap between the magnetic orbitals across the extended bis-bidentate L bridge in 3 and 4 account for their magnetic properties. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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13 pages, 2000 KiB  
Article
Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials
by Dong Joo Min, Kyunam Lee, Hyunji Park, Ji Eon Kwon and Soo Young Park
Molecules 2021, 26(4), 894; https://doi.org/10.3390/molecules26040894 - 8 Feb 2021
Cited by 16 | Viewed by 4974
Abstract
Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the [...] Read more.
Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E1/2) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Hammett constant of the substituents. In Li-ion coin cells, the discharge voltages of the s-tetrazine electrodes are successfully tuned depending on the electron-donating/withdrawing capabilities of the substituents. Furthermore, it is found that the heterogeneous electron transfer rate (k0) of the s-tetrazine molecules and Li-ion diffusivity (DLi) in the s-tetrazine electrodes are much faster than conventional electrode active materials. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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9 pages, 1558 KiB  
Article
Evaluation of [64Cu]Cu-NOTA-PEG7-H-Tz for Pretargeted Imaging in LS174T Xenografts—Comparison to [111In]In-DOTA-PEG11-BisPy-Tz
by Christian B. M. Poulie, Jesper T. Jørgensen, Vladimir Shalgunov, Georgios Kougioumtzoglou, Troels Elmer Jeppesen, Andreas Kjaer and Matthias M. Herth
Molecules 2021, 26(3), 544; https://doi.org/10.3390/molecules26030544 - 21 Jan 2021
Cited by 19 | Viewed by 3589
Abstract
Pretargeted nuclear imaging for the diagnosis of various cancers is an emerging and fast developing field. The tetrazine ligation is currently considered the most promising reaction in this respect. Monoclonal antibodies are often the preferred choice as pretargeting vector due to their outstanding [...] Read more.
Pretargeted nuclear imaging for the diagnosis of various cancers is an emerging and fast developing field. The tetrazine ligation is currently considered the most promising reaction in this respect. Monoclonal antibodies are often the preferred choice as pretargeting vector due to their outstanding targeting properties. In this work, we evaluated the performance of [64Cu]Cu-NOTA-PEG7-H-Tz using a setup we previously used for [111In]In-DOTA-PEG11-BisPy-Tz, thereby allowing for comparison of the performance of these two promising pretargeting imaging agents. The evaluation included a comparison of the physicochemical properties of the compounds and their performance in an ex vivo blocking assay. Finally, [64Cu]Cu-NOTA-PEG7-H-Tz was evaluated in a pretargeted imaging study and compared to [111In]In-DOTA-PEG11-BisPy-Tz. Despite minor differences, this study indicated that both evaluated tetrazines are equally suited for pretargeted imaging. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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13 pages, 2514 KiB  
Article
Concise Synthesis of Functionalized Cyclobutene Analogues for Bioorthogonal Tetrazine Ligation
by Jiayu Sun, Jie Li, Hongbao Sun, Chunling Li and Haoxing Wu
Molecules 2021, 26(2), 276; https://doi.org/10.3390/molecules26020276 - 8 Jan 2021
Viewed by 3527
Abstract
Novel bioorthogonal tools enable the development of new biomedical applications. Here we report the concise synthesis of a series of aryl-functionalized cyclobutene analogues using commercially available starting materials. Our study demonstrates that cyclobutene acts as a small, strained dienophile to generate stable substrates [...] Read more.
Novel bioorthogonal tools enable the development of new biomedical applications. Here we report the concise synthesis of a series of aryl-functionalized cyclobutene analogues using commercially available starting materials. Our study demonstrates that cyclobutene acts as a small, strained dienophile to generate stable substrates suitable for bioorthogonal tetrazine ligation. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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Review

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16 pages, 4560 KiB  
Review
Overview of Syntheses and Molecular-Design Strategies for Tetrazine-Based Fluorogenic Probes
by Sang-Kee Choi, Jonghoon Kim and Eunha Kim
Molecules 2021, 26(7), 1868; https://doi.org/10.3390/molecules26071868 - 26 Mar 2021
Cited by 40 | Viewed by 6971
Abstract
Various bioorthogonal chemistries have been used for fluorescent imaging owing to the advantageous reactions they employ. Recent advances in bioorthogonal chemistry have revolutionized labeling strategies for fluorescence imaging, with inverse electron demand Diels–Alder (iEDDA) reactions in particular attracting recent attention owing to their [...] Read more.
Various bioorthogonal chemistries have been used for fluorescent imaging owing to the advantageous reactions they employ. Recent advances in bioorthogonal chemistry have revolutionized labeling strategies for fluorescence imaging, with inverse electron demand Diels–Alder (iEDDA) reactions in particular attracting recent attention owing to their fast kinetics and excellent specificity. One of the most interesting features of the iEDDA labeling strategy is that tetrazine-functionalized dyes are known to act as fluorogenic probes. In this review, we will focus on the synthesis, molecular-design strategies, and bioimaging applications of tetrazine-functionalized fluorogenic probes. Traditional Pinner reaction and “Pinner-like” reactions for tetrazine synthesis are discussed here, as well as metal-catalyzed C–C bond formations with convenient tetrazine intermediates and the fabrication of tetrazine-conjugated fluorophores. In addition, four different quenching mechanisms for tetrazine-modified fluorophores are presented. Full article
(This article belongs to the Special Issue Tetrazines: A World of New Molecules Emerging from Old Chemistry)
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