Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry

Paolo Cerreia Vioglio, Luca Catalano, Vera Vasylyeva, Carlo Nervi, Michele Remo Chierotti, Giuseppe Resnati, Roberto Gobetto (Corresponding Author), Pierangelo Metrangolo

Research output: Contribution to journalArticleScientificpeer-review

19 Citations (Scopus)

Abstract

Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X-ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non-quadrupolar nuclei either directly involved in the interaction (15N) or covalently bonded to the halogen atom (13C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane were obtained. For the first time, the change in the 15N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. 13C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.
Original languageEnglish
Pages (from-to)16819–16828
JournalChemistry - A European Journal
Volume22
Issue number47
DOIs
Publication statusPublished - 2016
MoE publication typeA1 Journal article-refereed

Fingerprint

Halogens
Chemical shift
Nuclear magnetic resonance
Geometry
Single crystals
Crystals
Ethane
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Density functional theory
Elongation
X ray diffraction
Atoms
Experiments

Keywords

  • chemical shifts
  • CPMAS
  • halogen bonding
  • NMR spectroscopy
  • normalized distance parameter

Cite this

Cerreia Vioglio, P., Catalano, L., Vasylyeva, V., Nervi, C., Chierotti, M. R., Resnati, G., ... Metrangolo, P. (2016). Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry. Chemistry - A European Journal, 22(47), 16819–16828 . https://doi.org/10.1002/chem.201603392
Cerreia Vioglio, Paolo ; Catalano, Luca ; Vasylyeva, Vera ; Nervi, Carlo ; Chierotti, Michele Remo ; Resnati, Giuseppe ; Gobetto, Roberto ; Metrangolo, Pierangelo. / Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 47. pp. 16819–16828 .
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abstract = "Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X-ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non-quadrupolar nuclei either directly involved in the interaction (15N) or covalently bonded to the halogen atom (13C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane were obtained. For the first time, the change in the 15N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. 13C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.",
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Cerreia Vioglio, P, Catalano, L, Vasylyeva, V, Nervi, C, Chierotti, MR, Resnati, G, Gobetto, R & Metrangolo, P 2016, 'Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry', Chemistry - A European Journal, vol. 22, no. 47, pp. 16819–16828 . https://doi.org/10.1002/chem.201603392

Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry. / Cerreia Vioglio, Paolo; Catalano, Luca; Vasylyeva, Vera; Nervi, Carlo; Chierotti, Michele Remo; Resnati, Giuseppe; Gobetto, Roberto (Corresponding Author); Metrangolo, Pierangelo.

In: Chemistry - A European Journal, Vol. 22, No. 47, 2016, p. 16819–16828 .

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Natural abundance 15N and 13C solid-state NMR chemical shifts: high sensitivity probes of the halogen bond geometry

AU - Cerreia Vioglio, Paolo

AU - Catalano, Luca

AU - Vasylyeva, Vera

AU - Nervi, Carlo

AU - Chierotti, Michele Remo

AU - Resnati, Giuseppe

AU - Gobetto, Roberto

AU - Metrangolo, Pierangelo

PY - 2016

Y1 - 2016

N2 - Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X-ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non-quadrupolar nuclei either directly involved in the interaction (15N) or covalently bonded to the halogen atom (13C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane were obtained. For the first time, the change in the 15N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. 13C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.

AB - Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X-ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non-quadrupolar nuclei either directly involved in the interaction (15N) or covalently bonded to the halogen atom (13C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane were obtained. For the first time, the change in the 15N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. 13C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.

KW - chemical shifts

KW - CPMAS

KW - halogen bonding

KW - NMR spectroscopy

KW - normalized distance parameter

U2 - 10.1002/chem.201603392

DO - 10.1002/chem.201603392

M3 - Article

VL - 22

SP - 16819

EP - 16828

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 47

ER -