Isomorphous crystal structures of chlorodiacetylene and iododiacetylene derivatives: simultaneous hydrogen and halogen bonds on carbonyl

Baillargeon, Pierre; Rahem, Tarik; Caron-Duval, Édouard; Tremblay, Jacob; Fortin, Cloé; Blais, Étienne; Fan, Victor; Fortin, Daniel; Dory, Yves L.

doi:10.1107/s2056989017010155

Cited by 3 publications

(8 citation statements)

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“…Since terminal diacetylene, dibromodiacetylene, and diiododiacetylene − have been successfully used in topochemical polymerization experiments, this study could bring important data to understand the impact of the modulation of the terminal atom (H, Cl, Br, or I) on diacetylene polymerization and on the final optoelectronic properties of the resulting polyhalogenodiacetylene (PXDA). Since we have recently reported successfully a family of truly isomorphous crystal structures of DA and halogenoDA (XDA), , further studies are currently underway in our lab to complete the current study related with our new ClDA and PClDA with the parent terminal DA, bromodiacetylene, and iododiacetylene.…”

Section: Discussionmentioning

confidence: 99%

“…Our group reported in 2017 that derivatives of chlorodiacetylene (ClDA) can be easily prepared and recrystallized . Unfortunately, at this time, the packing arrangement of -(CC) 2 Cl group in the crystal structure was inappropriate for topochemical polymerization.…”

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confidence: 99%

“…Our group reported in 2017 that derivatives of chlorodiacetylene (ClDA) can be easily prepared and recrystallized. 71 Unfortunately, at this time, the packing arrangement of -(CC) 2 Cl group in the crystal structure was inappropriate for topochemical polymerization. Herein, we are pleased to present the first synthesis and SCXRD structure determinations of a ClDA derivative with nearly ideal stacking arrangement, and the resulting PClDA.…”

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confidence: 99%

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Rapid Access to Polychlorodiacetylene Single Crystals through H-Bond Templating and Computations on Helical PDA Oligomers

Baillargeon

Robidas

Legault

et al. 2020

Crystal Growth & Design

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Until now, only two structures of polyhalogenodiacetylene (PXDA) have been reported in the literature: polydiiododiacetylene (PDIDA) and polydibromodiacetylene (PDBDA). Herein we report the first example of the synthesis and topochemical polymerization of chlorodiacetylene (ClDA) to afford the single crystal X-ray diffraction (SCXRD) structure determination of polychlorodiacetylene (PClDA). A unique Hbonded network was exploited to achieve polymerization. The latter is parallel and close to the conjugated backbone, which constitutes the first clear single crystal example of this kind of system. Comparative DFT computational studies between the torsional potential on a model oligoClDA with the parent nonhalogenated compound were also performed. Finally, the capacity of the H-bonded network to induce helicity in the PDA chains was evaluated using semiempirical tight-binding calculations. The present work should contribute to the understanding of the exceptional optoelectronic properties of PDA associated with the presence of delocalized p-electrons in their backbone, with multiple possible sensing applications and electronic device conception, among many other possibilities.

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Section: Discussionmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Rapid Access to Polychlorodiacetylene Single Crystals through H-Bond Templating and Computations on Helical PDA Oligomers

Baillargeon

Robidas

Legault

et al. 2020

Crystal Growth & Design

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“…Examples of X-ray structures of 1-halopolyynes, especially homologues longer than butadiyne, are rather sparse. According to the CSD, for now only 1 structure containing the (CC) 2 Cl structural motif and 4 structures containing the (CC) 2 Br − motif are known. Moreover, 11 structures with the (CC) 2 I motif ,− and 3 with the (CC) 3 I , motif have been reported.…”

Section: Introductionmentioning

confidence: 99%

“…According to the CSD, for now only 1 structure containing the (CC) 2 Cl structural motif and 4 structures containing the (CC) 2 Br − motif are known. Moreover, 11 structures with the (CC) 2 I motif ,− and 3 with the (CC) 3 I , motif have been reported. Except for one 1-iodobutadiyne structure, all the others are different cocrystals of I(CC) n I ( n = 2, 3).…”

Section: Introductionmentioning

confidence: 99%

Crystal Engineering of 1-Halopolyynes by End-Group Manipulation

Pigulski

Gulia

Męcik

et al. 2019

Crystal Growth & Design

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Polyynes are compounds with two or more conjugated carbon–carbon triple bonds. Such molecules are usually regarded as models of carbynea hypothetical one-dimensional allotropic form of carbon. 1-Halopolyynes are rare representatives of such species, but few interesting crystal-to-crystal reactions have been recently reported for them. Herein, we present 11 new X-ray structures of 1-halopolyynes, nearly doubling the number of such compounds characterized with the use of single-crystal X-ray diffraction. The influence of an end-group on packing motifs in crystal structures of the 1-halopolyynes were thoroughly examined. Especially the strength of halogen bond as a function of polyyne chain length was analyzed with the support of theoretical calculations. Moreover, the compound CNC 8 I is the longest 1-halopolyyne characterized to date with the use of rentgenostructural analysis. In addition to that, the compounds NO 2 C 6 Br and MeC(O)C 6 Br are the first 1-bromohexatriynes characterized by means of X-ray single-crystal diffraction.

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Exploiting Unsaturated Carbon–Iodine Compounds for the Preparation of Carbon-Rich Materials

2019

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CONSPECTUS: Conjugated carbon-rich materials have drawn much academic and industrial attention in recent years, due to their intriguing electronic and optical properties and potential applications including organic photovoltaics, flexible and wearable electronics, and chemical and biological sensors. Unsaturated carbon−iodine compounds, mainly the derivatives of iodoalkenes and iodoalkynes, are a class of molecules in which iodine atoms are directly connected to unsaturated carbons. These compounds provide unique advantages in the pursuit of carbon-rich materials, largely due to the Lewis acidity of iodine atoms and the lability of the carbon−iodine bonds. The Lewis acidity and electrophilicity of iodine in unsaturated carbon−iodine compounds make them excellent donors of halogen bonding, which is an attractive interaction between the electrophilic halogen atoms and Lewis basic species. Halogen bonding has emerged as a reliable building block in crystal engineering and supramolecular architectures. In this Account, we illustrate examples of the controlled assembly of diiodopolyynes within host−guest cocrystals that contain oxalamide or urea hosts with appropriate Lewis basic end groups and diiodobutadiyne or diiodohexatriyne guests. Halogen bonding interactions between the host and guest result in an ordered alignment of the diiodopolyynes that allows for a solid-state topochemical polymerization. We have used this approach to prepare poly(diiododiacetylene), PIDA, and poly(iodoethynyliododiacetylene), PIEDA, two conjugated polymers composed only of carbon and iodine. In addition, the polarity of the carbon−iodine bond gives unsaturated carbon−iodine compounds an electron-rich π-system, permitting electrophilic addition reactions with molecular halogens. The halogenated products of these additions can then serve as precursors to other conjugated carbon-rich systems. The lability of the carbon−iodine bond, together with the polarizability of iodine and the higher electronegativity of sp-and sp 2hybridized carbons, open up further possibilities in pursuing novel carbon nanomaterials from unsaturated carbon−iodine compounds. For example, we have developed an iterative method for the synthesis of longer symmetric polyynes from shorter diiodopolyynes, using Stille coupling to the iodine-capped polyynes. The iodination/coupling cycle symmetrically lengthens the polyyne chain by two carbon−carbon triple bonds. This method is particularly helpful for preparing polyynes with an odd number of carbon−carbon triple bonds. In addition, the lability of the carbon−iodine bonds of PIDA leads to facile carbonization by pyrolysis or laser irradiation. More strikingly, diiodoalkenes undergo quantitative elimination of iodine in the presence of Lewis bases. This reaction can be used to eliminate iodine at room temperature from PIDA, in which the carbon− iodine bonds are much more easily broken than in the diiodopolyynes, resulting in graphitic carbon materials.

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Isomorphous crystal structures of chlorodiacetylene and iododiacetylene derivatives: simultaneous hydrogen and halogen bonds on carbonyl

Cited by 3 publications

References 32 publications

Rapid Access to Polychlorodiacetylene Single Crystals through H-Bond Templating and Computations on Helical PDA Oligomers

Rapid Access to Polychlorodiacetylene Single Crystals through H-Bond Templating and Computations on Helical PDA Oligomers

Crystal Engineering of 1-Halopolyynes by End-Group Manipulation

Exploiting Unsaturated Carbon–Iodine Compounds for the Preparation of Carbon-Rich Materials

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