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Dichloro-4'-(2-Thienyl)-2,2':6',2 -Terpyridine

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Dichloro-4'-(2-Thienyl)-2,2':6',2 -Terpyridine 4,4-Dichloro-4’-(2-thienyl)-2,2’:6’,2-terpyridine Jérôme Husson, Laurent Guyard To cite this version: Jérôme Husson, Laurent Guyard. 4,4-Dichloro-4’-(2-thienyl)-2,2’:6’,2-terpyridine. Molbank, MDPI, 2019, 2019 (3), pp.M1071. 10.3390/M1071. hal-02294577 HAL Id: hal-02294577 https://hal.archives-ouvertes.fr/hal-02294577 Submitted on 17 Dec 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution - NoDerivatives| 4.0 International License molbank Short Note Short Note 4,4′′-Dichloro-40′-(2-thienyl)-2,20′:6′0,2′′-terpyridine 4,4”-Dichloro-4 -(2-thienyl)-2,2 :6 ,2”-terpyridine Jérôme Husson * and Laurent Guyard JéInstitutrômeHusson UTINAM * UMRand CNRS Laurent 6213, Guyard Université de Bourgogne-Franche-Comté, 16 route de Gray, 25030 InstitutBesançon UTINAM cedex, France UMR CNRS 6213, Université de Bourgogne-Franche-Comté, 16 route de Gray, 25030* Correspondence: Besançon CEDEX, [email protected]; France Tel.: +33-3-81666291 * Correspondence: [email protected]; Tel.: +33-3-81666291 Received: 25 June 2019; Accepted: 4 July 2019; Published: 9 July 2019 Received: 25 June 2019; Accepted: 4 July 2019; Published: 9 July 2019 Abstract: A new thiophene-substituted terpyridine derivative has been prepared and characterized. Abstract:This ligandA features new thiophene-substituted a thiophene heterocycle terpyridine (as an electrochemically derivative has been polymerizable prepared and unit) characterized. as well as Thistwo chlorine ligand features atoms for a thiophene further functionalization. heterocycle (as an electrochemically polymerizable unit) as well as two chlorine atoms for further functionalization. Keywords: ligand; pyridine derivatives; thiophene derivatives Keywords: ligand; pyridine derivatives; thiophene derivatives 1. Introduction 1. Introduction Terpyridine (terpy) derivatives (especially 2,2’:6’,2’’-terpyridines) and their complexes have beenTerpyridine widely studied (terpy) [1]. derivatives In fact, an (especially important 2,2 number0:60,2”-terpyridines) of terpyridine-based and their complexes compounds have can been be widelyprepared studied by varying [1]. In the fact, substitution an important pattern number onto of the terpyridine-based terpyridine scaffold compounds and/or the can nature be prepared of the bycomplexed varying themetal. substitution Terpyridines pattern and ontotheir the complexes terpyridine have sca foundffold anda vast/or range the nature of applications of the complexed such as metal.sensitizers Terpyridines in solar cells and [2], their catalysts complexes [3], materials have found for a water vast range treatment of applications [4], electrochromic such as sensitizers materials in[5], solar or as cells chromophores [2], catalysts [6], [3 ],just materials to name for a few. water Terpyridine treatment [complexes4], electrochromic that are materialssubstituted [5 ],with or as a chromophoresthiophene ring [ 6are], just interesting to name a compounds few. Terpyridine because complexes they also that arefind substituted many possible with aapplications thiophene ring in arematerial interesting science compounds [7] or medicinal because chemistry they also and find biol manyogy [8,9], possible for example. applications Especially, in material the sciencethiophene [7] orheterocycle medicinal allows chemistry for the and formation biology of [8, polymeric9], for example. materials Especially, through the electrochemical thiophene heterocycle polymerization. allows forThe the so formationobtained terpyridine-containi of polymeric materialsng materials through electrochemicalhave shown potentia polymerization.l uses as sensors The so [10] obtained or as terpyridine-containingelectrochromic materials materials [11], for ex haveample. shown Therefore, potential the synthesis uses as sensors of new terpy [10] or derivatives as electrochromic that bear materialsa pendant [ 11thiophene], for example. ring is Therefore, still of interest. the synthesis This article of new follows terpy derivatives our previous that work bear aon pendant furan- thiophenecontaining ring terpy is still[12] ofand interest. describes This the article synthesis follows and our characterization previous work of on 4,4 furan-containing′′-dichloro-4′-(2-thienyl)- terpy [12] and2,2′:6 describes′,2′′-terpyridine the synthesis (1) (Figure and 1). characterization This ligand not of only 4,4”-dichloro-4 features a 0thiophene-(2-thienyl)-2,2 ring 0but:60,2”-terpyridine also possesses (two1) (Figure chlorine1). Thisatoms ligand on the not outer only featurespyridine a thiophenerings, which ring allow but also for possessesfuture functionalization two chlorine atoms of this on theterpyridine. outer pyridine rings, which allow for future functionalization of this terpyridine. FigureFigure 1.1. StructureStructure andand atomatom numberingnumbering ofof 4,4”-dichloro-44,4′′-dichloro-40′-(2-thienyl)-2,2-(2-thienyl)-2,20′:60′,2,2”-terpyridine′′-terpyridine ( (11).). 2. Results and Discussion 2. Results and Discussion Amongst all methods available for the preparation of terpyridine derivatives [13–15], the one fromMolbank Wang 2019, 2019 and, x; Hanandoi: [16] was selected, although sometimes this methodwww.mdpi.c failsom/journal/molbank in producing Molbank 2019, 2019, M1071; doi:10.3390/M1071 www.mdpi.com/journal/molbank Molbank 2019, 2019, M9xx 2 of 5 Molbank 2019, 2019, M9xx 2 of 5 MolbankAmongst2019, 2019 all, M1071 methods available for the preparation of terpyridine derivatives [13–15], the 2one of 5 fromAmongst Wang and all methodsHanan [16] available was selected, for the preparationalthough sometimes of terpyridine this derivativesmethod fails [13–15], in producing the one fromterpyridine Wang derivativesand Hanan [17]. [16] Thus was 1 selected,was simply althou preparedgh sometimes by mixing this 4-chloro-2-acetylpyridine method fails in producing [18], terpyridinethiophene-2-carboxaldehyde, derivatives [17]. [17]. Thus Thusand potassium11 was simply hydrox prepared ide in ethanolby mixing and 4-chloro-2-acetylpyridine aqueous ammonia (Figure [18], [18 2).], thiophene-2-carboxaldehyde, and potassium hydroxidehydroxide in ethanol and aqueous ammonia (Figure2 2).). Figure 2. Preparation of terpyridine (Compound 1). Figure 2. Preparation of terpyridine (Compound 1). Crude 1 precipitated from the reaction mixture and was isolated by simple filtration. At this Crude 1 precipitated from the reaction mixture and was isolated by simple filtration. At this point, point,Crude the material 1 precipitated collected from was the sufficiently reaction mixturepure (>98% and bywas quantitative isolated by NMR simple [19]) filtration. to be used At this for the material collected was sufficiently pure (>98% by quantitative NMR [19]) to be used for further point,further the experiments material collected (e.g., preparation was sufficiently of metal pure complexes) (>98% by without quantitative purification. NMR [19]) to be used for experiments (e.g., preparation of metal complexes) without purification. furtherThe experiments identity of (e.g.,compound preparation 1 was of confirmed metal complexes) by different without anal purification.ytical techniques. Firstly, NMR The identity of compound 1 was confirmed by different analytical techniques. Firstly, NMR spectraThe ( 1Hidentity and 13 C)of compoundagreed with 1 the was chemical confirmed structure. by different Especially, analytical the singlet techniques. for proton Firstly, 3′ andNMR 5′ spectra (1H and 13C) agreed with the chemical structure. Especially, the singlet for proton 3 and 5 spectrawas clearly (1H seenand 13atC) δ agreed= 8.72 ppm. with Furthermore, the chemical signalsstructure. for Especially,protons 3, 3 the′′, 6, singlet and 6′′ forwere proton merged 30′ and into 5 a0′ was clearly seen at δ = 8.72 ppm. Furthermore, signals for protons 3, 3”, 6, and 6” were merged into a wasmultiplet clearly while seen protons at δ = 8.72 5 and ppm. 5′′ appearedFurthermore, as a doubletsignals forof doublet protons (Figure 3, 3′′, 6, 3). and Such 6′′ werean 1H merged NMR pattern into a multiplet while protons 5 and 5” appeared as a doublet of doublet (Figure3). Such an 1H NMR pattern multiplethas been alreadywhile protons observed 5 and for 5 4,4′′ appeared′′-dichloro-2,2 as a doublet′:6′,2′′-terpyridine of doublet (Figure[20]. 3). Such an 1H NMR pattern has been already observed for 4,4”-dichloro-2,24,4′′-dichloro-2,20′:6:6′0,2,2”-terpyridine′′-terpyridine [20]. [20]. Figure 3. Part of NMR spectrum showing signals for protons (30,50), (3,3”,60,6”), and (5,5”). Figure 3. Part of NMR spectrum showing signals for protons (3′,5′), (3,3′′,6′,6′′), and (5,5′′). Additionally,Figure 3. Part the of formation NMR spectrum of the showing title compound signals for was protons confirmed (3′,5′), (3,3 by′′,6 HR-MS′,6′′), and (Figure (5,5′′). S3) since + the [MAdditionally,+ H] ion the peak, formation as well of as the the title isotopic compound distribution, was confirmed corresponded by HR-MS to molecular (Figure S3) formula since + (Cthe19 H[MAdditionally,12
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