Rotational dynamics of diazabicyclo[2.2.2]octane in isomorphous halogen-bonded co-crystals

Entropic and enthalpic effects

Luca Catalano, Salvador Perez-Estrada, Hsin Hua Wang, Anoklase J.L. Ayitou, Saeed I. Khan, Giancarlo Terraneo, Pierangelo Metrangolo, Stuart Browne, Miguel A. Garcia-Garibay

Research output: Contribution to journalArticleScientificpeer-review

28 Citations (Scopus)

Abstract

Based on rotational dynamics measurements carried out with isomorphic co-crystals formed by halogenbonding (XB) between tritylacetylene halides (TrX) and diazabicyclo[2.2.2]octane (dabco), we were able to distinguish the sources of the enthalpic and entropie components in the rotational free energy barrier. We describe the formation of the 1:1 co-crystals (TrX···N(R)3N) obtained from 1 equiv of dabco and 1 equiv of either Tri or TrBr, respectively, to give 4a and 4b instead of the potential 2:1 complexes. The co-crystals were prepared by solvent evaporation and mechanochemical synthesis. No co-crystal with TrCl was obtained, reflecting the weaker nature of the TrCl···NR3 interaction. Single-crystal X-ray diffraction confirmed structures that resemble a spinning top on a tripod and revealed that the two XB co-crystals are isomorphous, with slightly different C-X···NR3 (X = I, Br) distances and packing interactions. Quadrupolar-echo2H NMR experiments with2H-labeled samples showed that fast rotation of dabco in these co-crystals follows a six-fold potential energy surface with three lowest energy minima. Variable-temperature 1H NMR spin-lattice relaxation (VT 1H T1) data revealed rotational dynamics with indistinguishable pre-exponential factors and small but distinguishable activation energies. The activation energy of 4b (Ea = 0.71 kcal mol-1) is the lowest reported in the field of amphidynamic crystals. Using the Eyring equation, we established that their activation entropy for rotation is small but negative (ΔS = -3.0 cal mol-1 K-1), while there is almost a 2-fold difference in activation enthalpies, with 4a having a higher barrier (ΔH = 0.95 kcal mol-1) than 4b (ΔH = 0.54 kcal mol-1)-Analysis of the rotator cavity in the two co-crystals revealed subtle differences in steric interactions that account for their different activation energies.

Original languageEnglish
Pages (from-to)843-848
Number of pages6
JournalJournal of the American Chemical Society
Volume139
Issue number2
DOIs
Publication statusPublished - 18 Jan 2017
MoE publication typeA1 Journal article-refereed

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Halogens
Crystals
Entropy
X-Ray Diffraction
Temperature
Activation energy
Chemical activation
Nuclear magnetic resonance
Potential energy surfaces
Spin-lattice relaxation
diazabicyclo(2.2.2)octane
Energy barriers
Free energy
Enthalpy
Evaporation
Single crystals
X ray diffraction
Proton Magnetic Resonance Spectroscopy

Cite this

Catalano, L., Perez-Estrada, S., Wang, H. H., Ayitou, A. J. L., Khan, S. I., Terraneo, G., ... Garcia-Garibay, M. A. (2017). Rotational dynamics of diazabicyclo[2.2.2]octane in isomorphous halogen-bonded co-crystals: Entropic and enthalpic effects. Journal of the American Chemical Society, 139(2), 843-848. https://doi.org/10.1021/jacs.6b10780
Catalano, Luca ; Perez-Estrada, Salvador ; Wang, Hsin Hua ; Ayitou, Anoklase J.L. ; Khan, Saeed I. ; Terraneo, Giancarlo ; Metrangolo, Pierangelo ; Browne, Stuart ; Garcia-Garibay, Miguel A. / Rotational dynamics of diazabicyclo[2.2.2]octane in isomorphous halogen-bonded co-crystals : Entropic and enthalpic effects. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 2. pp. 843-848.
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abstract = "Based on rotational dynamics measurements carried out with isomorphic co-crystals formed by halogenbonding (XB) between tritylacetylene halides (TrX) and diazabicyclo[2.2.2]octane (dabco), we were able to distinguish the sources of the enthalpic and entropie components in the rotational free energy barrier. We describe the formation of the 1:1 co-crystals (TrX···N(R)3N) obtained from 1 equiv of dabco and 1 equiv of either Tri or TrBr, respectively, to give 4a and 4b instead of the potential 2:1 complexes. The co-crystals were prepared by solvent evaporation and mechanochemical synthesis. No co-crystal with TrCl was obtained, reflecting the weaker nature of the TrCl···NR3 interaction. Single-crystal X-ray diffraction confirmed structures that resemble a spinning top on a tripod and revealed that the two XB co-crystals are isomorphous, with slightly different C-X···NR3 (X = I, Br) distances and packing interactions. Quadrupolar-echo2H NMR experiments with2H-labeled samples showed that fast rotation of dabco in these co-crystals follows a six-fold potential energy surface with three lowest energy minima. Variable-temperature 1H NMR spin-lattice relaxation (VT 1H T1) data revealed rotational dynamics with indistinguishable pre-exponential factors and small but distinguishable activation energies. The activation energy of 4b (Ea = 0.71 kcal mol-1) is the lowest reported in the field of amphidynamic crystals. Using the Eyring equation, we established that their activation entropy for rotation is small but negative (ΔS‡ = -3.0 cal mol-1 K-1), while there is almost a 2-fold difference in activation enthalpies, with 4a having a higher barrier (ΔH‡ = 0.95 kcal mol-1) than 4b (ΔH‡ = 0.54 kcal mol-1)-Analysis of the rotator cavity in the two co-crystals revealed subtle differences in steric interactions that account for their different activation energies.",
author = "Luca Catalano and Salvador Perez-Estrada and Wang, {Hsin Hua} and Ayitou, {Anoklase J.L.} and Khan, {Saeed I.} and Giancarlo Terraneo and Pierangelo Metrangolo and Stuart Browne and Garcia-Garibay, {Miguel A.}",
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Catalano, L, Perez-Estrada, S, Wang, HH, Ayitou, AJL, Khan, SI, Terraneo, G, Metrangolo, P, Browne, S & Garcia-Garibay, MA 2017, 'Rotational dynamics of diazabicyclo[2.2.2]octane in isomorphous halogen-bonded co-crystals: Entropic and enthalpic effects', Journal of the American Chemical Society, vol. 139, no. 2, pp. 843-848. https://doi.org/10.1021/jacs.6b10780

Rotational dynamics of diazabicyclo[2.2.2]octane in isomorphous halogen-bonded co-crystals : Entropic and enthalpic effects. / Catalano, Luca; Perez-Estrada, Salvador; Wang, Hsin Hua; Ayitou, Anoklase J.L.; Khan, Saeed I.; Terraneo, Giancarlo; Metrangolo, Pierangelo; Browne, Stuart; Garcia-Garibay, Miguel A.

In: Journal of the American Chemical Society, Vol. 139, No. 2, 18.01.2017, p. 843-848.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Rotational dynamics of diazabicyclo[2.2.2]octane in isomorphous halogen-bonded co-crystals

T2 - Entropic and enthalpic effects

AU - Catalano, Luca

AU - Perez-Estrada, Salvador

AU - Wang, Hsin Hua

AU - Ayitou, Anoklase J.L.

AU - Khan, Saeed I.

AU - Terraneo, Giancarlo

AU - Metrangolo, Pierangelo

AU - Browne, Stuart

AU - Garcia-Garibay, Miguel A.

PY - 2017/1/18

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N2 - Based on rotational dynamics measurements carried out with isomorphic co-crystals formed by halogenbonding (XB) between tritylacetylene halides (TrX) and diazabicyclo[2.2.2]octane (dabco), we were able to distinguish the sources of the enthalpic and entropie components in the rotational free energy barrier. We describe the formation of the 1:1 co-crystals (TrX···N(R)3N) obtained from 1 equiv of dabco and 1 equiv of either Tri or TrBr, respectively, to give 4a and 4b instead of the potential 2:1 complexes. The co-crystals were prepared by solvent evaporation and mechanochemical synthesis. No co-crystal with TrCl was obtained, reflecting the weaker nature of the TrCl···NR3 interaction. Single-crystal X-ray diffraction confirmed structures that resemble a spinning top on a tripod and revealed that the two XB co-crystals are isomorphous, with slightly different C-X···NR3 (X = I, Br) distances and packing interactions. Quadrupolar-echo2H NMR experiments with2H-labeled samples showed that fast rotation of dabco in these co-crystals follows a six-fold potential energy surface with three lowest energy minima. Variable-temperature 1H NMR spin-lattice relaxation (VT 1H T1) data revealed rotational dynamics with indistinguishable pre-exponential factors and small but distinguishable activation energies. The activation energy of 4b (Ea = 0.71 kcal mol-1) is the lowest reported in the field of amphidynamic crystals. Using the Eyring equation, we established that their activation entropy for rotation is small but negative (ΔS‡ = -3.0 cal mol-1 K-1), while there is almost a 2-fold difference in activation enthalpies, with 4a having a higher barrier (ΔH‡ = 0.95 kcal mol-1) than 4b (ΔH‡ = 0.54 kcal mol-1)-Analysis of the rotator cavity in the two co-crystals revealed subtle differences in steric interactions that account for their different activation energies.

AB - Based on rotational dynamics measurements carried out with isomorphic co-crystals formed by halogenbonding (XB) between tritylacetylene halides (TrX) and diazabicyclo[2.2.2]octane (dabco), we were able to distinguish the sources of the enthalpic and entropie components in the rotational free energy barrier. We describe the formation of the 1:1 co-crystals (TrX···N(R)3N) obtained from 1 equiv of dabco and 1 equiv of either Tri or TrBr, respectively, to give 4a and 4b instead of the potential 2:1 complexes. The co-crystals were prepared by solvent evaporation and mechanochemical synthesis. No co-crystal with TrCl was obtained, reflecting the weaker nature of the TrCl···NR3 interaction. Single-crystal X-ray diffraction confirmed structures that resemble a spinning top on a tripod and revealed that the two XB co-crystals are isomorphous, with slightly different C-X···NR3 (X = I, Br) distances and packing interactions. Quadrupolar-echo2H NMR experiments with2H-labeled samples showed that fast rotation of dabco in these co-crystals follows a six-fold potential energy surface with three lowest energy minima. Variable-temperature 1H NMR spin-lattice relaxation (VT 1H T1) data revealed rotational dynamics with indistinguishable pre-exponential factors and small but distinguishable activation energies. The activation energy of 4b (Ea = 0.71 kcal mol-1) is the lowest reported in the field of amphidynamic crystals. Using the Eyring equation, we established that their activation entropy for rotation is small but negative (ΔS‡ = -3.0 cal mol-1 K-1), while there is almost a 2-fold difference in activation enthalpies, with 4a having a higher barrier (ΔH‡ = 0.95 kcal mol-1) than 4b (ΔH‡ = 0.54 kcal mol-1)-Analysis of the rotator cavity in the two co-crystals revealed subtle differences in steric interactions that account for their different activation energies.

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U2 - 10.1021/jacs.6b10780

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