Anion templated crystal engineering of halogen bonding tripodal tris(halopyridinium) compounds

Foyle, Emer; White, Nicholas G.

doi:10.1039/d0ce00241k

Cited by 16 publications

(30 citation statements)

References 47 publications

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“…As shown in Figure 2, the iodine atoms of the TTF are engaged in directional interactions with the chloride anion (ffCÀ I•••Cl À = 174-175°), with I•••Cl À distances (2.96-2.97 Å) much shorter than the contact distance (3.79 Å) determined as the sum of iodine van der Waals radius (1.98 Å) and chloride ionic radius (1.81 Å), giving a reduction ratio (RR) well below 0.8 (0.78). This represents one of the shortest I•••Cl À XB interaction reported so far [16,17] and the shortest one involving iodinated TTFs. The chloride is interacting with two iodine atoms giving then a kind of μ 2 "coordination" around the halide.…”

Section: Structural Properties: Intermolecular Interactionsmentioning

confidence: 68%

Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives

et al. 2020

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Halogen bonding (XB) interactions are investigated in cation radical salts of bis(methylthio)-5,5'-diiodotetrathiafulvalene (1). Electrocrystallization of 1 in the presence of Bu 4 NCl affords a 1 : 1 salt formulated as (E-1)Cl. Particularly strong I•••Cl À XB interactions are observed around the Cl À anion with the distances at 78 % the sum of the van der Waals radii, a consequence of the XB charge activation in the cation radical. Moreover, the Cl À environment is complemented by two extra S•••Cl À chalcogen bonding (ChB) interactions, an original feature among reported halide salts of TTF derivatives. Electrostatic potential calculations on the cation radical further demonstrate the efficient activation of the S atoms of the 1,3-dithiole rings (V s,max = 87.2 kcal/mol), as strong as with the iodine atoms (V s,max = 87.9 kcal/mol). The radical cations form weakly dimerized stacks, as confirmed by the variable-temperature magnetic susceptibility and the weak conductivity (4.8 × 10 À 5 S cm À 1).

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Section: Structural Properties: Intermolecular Interactionsmentioning

confidence: 68%

Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives

et al. 2020

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“…As chloride anions are potentially coordinating and may interfere with the self-assembly process, we exchanged these for non-coordinating BPh 4 -anions in quantitative yield. We attempted to prepare 2 31 in an analogous manner using a Suzuki coupling of tris-bromomethyl compound 5 [36] and 4-cyanophenylboronic acid in conditions similar to those reported by Kotha et al [37] We were able to prepare the new tris-nitrile 6, albeit in relatively low yield (27 %). However, attempts to convert this into the tris-amidinium 2 31 were unsuccessful with a mixture of products being observed: mass spectrometry and NMR spectroscopy indicated that some product was formed but we were not able to isolate this or drive the reaction to completion.…”

Section: Synthesis Of Tectonsmentioning

confidence: 89%

“…The tetraphenyl tris-alkyne 3, [35] the tris(hexyloxy)benzene trisbromomethyl compound 5, [36] bis-amidinium 8 . (BPh 4 ) 2 , [28] TBA 2 .…”

Section: General Remarksmentioning

confidence: 99%

An Investigation of Five Component [3+2] Self-Assembled Cage Formation Using Amidinium···Carboxylate Hydrogen Bonds

et al. 2021

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The assembly of hydrogen bonded cages using amidiniumÁÁÁcarboxylate hydrogen bonding interactions was investigated. A new tris-amidinium hydrogen bond donor tecton based on a tetraphenylmethane scaffold was prepared and its selfassembly with the terephthalate anion studied, and a new tricarboxylate hydrogen bond acceptor tecton was synthesised and its assembly with the 1,3-benzenebis(amidinium) hydrogen bond donor explored. In both cases, molecular modelling indicated that the formation of the cages was geometrically feasible and 1 H NMR spectroscopic evidence was consistent with interactions between the components in competitive d 6 -DMSO solvent mixtures. DOSY NMR spectroscopy of both systems indicated that both components diffuse at the same rate as each other, and diffusion coefficients were consistent with cage formation, and with the formation of assemblies significantly larger than the individual components. An X-ray crystal structure showed that one of the assemblies did not have the desired cage structure in the solid state.

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“…We attempted to prepare 2 3+ in an analogous manner using a Suzuki coupling of tris-bromomethyl compound 5 35 and 4-cyanophenylboronic acid in conditions similar to those reported by Kotha. 36 We were able to prepare the new tris-nitrile 6, albeit in relatively low yield (27%).…”

Section: Synthesis Of Tectonsmentioning

confidence: 99%

“…The tetraphenyl tris-alkyne 3, 34 the tris(hexyloxy)benzene tris-bromomethyl compound 5, 35 bis-amidinium 8•(BPh4)2, 28 TBA2•TP, 40 and TBA2•IP 28 were prepared as previously described. Dry THF was distilled from sodium prior to use, other chemicals were brought from commercial suppliers and used as received.…”

Section: Experimental General Remarksmentioning

confidence: 99%

An Investigation of Five Component [3+2] Self-Assembled Cage Formation Using amidinium...carboxylate Hydrogen Bonds

Thomas¹,

Foyle²,

Walker³

et al. 2021

Preprint

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The assembly of hydrogen bonded cages using amidinium∙∙∙carboxylate hydrogen bonding interactions was investigated. A new tris-amidinium hydrogen bond donor tecton based on a tetraphenylmethane scaffold was prepared and its self–assembly with the terephthalate anion studied, and a new tricarboxylate hydrogen bond acceptor tecton was synthesized and its assembly with the 1,3-benzenebis(amidinium) hydrogen bond donor explored. In both cases, molecular modelling indicated that the formation of the cages was geometrically feasible and 1H NMR spectroscopic evidence was consistent with interactions between the components in competitive d6- DMSO solvent mixtures. DOSY NMR spectroscopy of both systems indicated that both components diffuse at the same rate as each other, and diffusion coefficients were consistent with cage formation, and with the formation of assemblies significantly larger than the individual components. An X-ray crystal structure showed that one of the assemblies did not have the desired cage structure in the solid state

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Anion templated crystal engineering of halogen bonding tripodal tris(halopyridinium) compounds

Abstract: Crystal engineering of halogen bonding tripodal receptors is found to be highly dependent on solvent and choice of anion.

Cited by 16 publications

References 47 publications

Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives

Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives

An Investigation of Five Component [3+2] Self-Assembled Cage Formation Using Amidinium···Carboxylate Hydrogen Bonds

An Investigation of Five Component [3+2] Self-Assembled Cage Formation Using amidinium...carboxylate Hydrogen Bonds

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