Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Ciancaleoni, Gianluca

doi:10.3390/magnetochemistry3040030

Cited by 14 publications

(16 citation statements)

References 108 publications

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“…Nevertheless, also amylose-based CSPs proved to be useful in this field allowing to assess steric effects on XBs. Finally, as spectroscopic techniques have been widely used in this field [12], ESR and NMR spectroscopy experiments were carried out (Supporting Information) to gain an insight into the sensitivity of the techniques toward some 4,4 ′bipyridyl XBD probes. These experiments poorly confirmed the XBD activity proving the higher sensitivity of HPLC for detection of weak stereoselective XBs in solution.…”

Section: A Novel Strategy For Detection Of Stereoselective -Hole Bondmentioning

confidence: 99%

“…Another open issue concerns the application of XB in chiral systems, and few chiral molecules having σ-holes on halogens as recognition sites were described recently [5][6][7][8][9][10][11]. Perfluorinated and cationic N-heterocyclic substructures ( Figure 1B) are able to activate potential σ-hole sites and generate strong XBs, which are detectable by means of a variety of spectroscopic techniques, of which NMR spectroscopy is the most widely used [12]. On the other hand, iodinated and brominated neutral XB donors (XBDs) lacking perfluorination are needed for real-life applications in drug design [13] and supramolecular chemistry [14].…”

Section: Introductionmentioning

confidence: 99%

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Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Peluso

Mamane

Dallocchio

et al. 2018

J of Separation Science

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In the last few years, halogen bonds have been exploited in a variety of research areas both in the solid state and in solution. Nevertheless, several factors make formation and detection of halogen bonds in solution challenging. Moreover, to date, few chiral molecules containing electrophilic halogens as recognition sites have been reported. Recently, we described the first series of halogen-bond-driven enantioseparations performed on cellulose tris(3,5-dimethylphenylcarbamate) by high-performance liquid chromatography. Herein the performances of amylose tris(3,5-dimethylphenylcarbamate) as halogen bond acceptor were also investigated and compared with respect to cellulose tris(3,5-dimethylphenylcarbamate). With the aim to explore the effect of polysaccharide backbone on the enantioseparations, the thermodynamic parameters governing the halogen-dependent enantioseparations on both cellulose and amylose polymers were determined by a study at variable temperature and compared. Molecular dynamics were performed to model the halogen bond in polysaccharide-analyte complexes. Chiral halogenated 4,4'-bipyridines were used as test compounds (halogen bond donors). On this basis, a practical method for detection of stereoselective halogen bonds in solution was developed, which is based on the unprecedented use of high-performance liquid chromatography as technical tool with polysaccharide polymers as molecular probes (halogen bond acceptors). The analytical strategy showed higher sensitivity for the detection of weak halogen bonds.

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Section: A Novel Strategy For Detection Of Stereoselective -Hole Bondmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Peluso

Mamane

Dallocchio

et al. 2018

J of Separation Science

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“…In adducing evidence for halogen bonding a variety of theoretical studies have been reported, besides experimental structural studies in solution and solid state . NMR– and ESR investigations are among major experimental techniques employed in recent times. In particular, one may mention NMR chemical shift titration, heteronuclear Overhauser effect (NOE) measurements, as well as NMR self‐diffusion measurements on halogen bonded complexes.…”

Section: Figurementioning

confidence: 99%

“…NMR– and ESR investigations are among major experimental techniques employed in recent times. In particular, one may mention NMR chemical shift titration, heteronuclear Overhauser effect (NOE) measurements, as well as NMR self‐diffusion measurements on halogen bonded complexes. ESR studies have typically involved a nitroxide free radical that doubles up as the nucleophile .…”

Section: Figurementioning

confidence: 99%

Motional Dynamics of Halogen‐Bonded Complexes Probed by Low‐Field NMR Relaxometry and Overhauser Dynamic Nuclear Polarization

Banerjee

Dey

Chandrakumar

2019

Chemistry An Asian Journal

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Halogen bonding is asubject of considerable interest owing to wide-ranging chemical, materials and biological applications. The motional dynamics of halogenbonded complexes play ap ivotalr ole in comprehending the nature of the halogen-bonding interaction. However, not many attempts appear to have been made to shed light on the dynamical characteristics of halogen-bonded species. For the first time, we demonstrateh ere that the combination of low-field NMR relaxometry andO verhauser dynamic nuclear polarization (ODNP) makes it possible to obtain ac ogentp icture of the motional dynamics of halogen-bonded species. We discussh ere the advantages of this combined approach. Low-field relaxometry allows us to infer the hydrodynamic radius and rotational correlation time, whereas ODNP probest he molecular translational correlation times (involving the substrate as well as the organic radical) with high sensitivity at low field. Noncovalent interactions are among the most discussed and debated areas in contemporaryc hemistry and biology.S everal experimentala nd theoretical efforts have been made to characterizea nd classify these interactions.A mong several such interactions H-bonding, halogenb onding, etc. play an important role in chemistry. [1] Halogen bonding (XB) has been defined as an attractive interaction between an electrophilicr egion aroundahalogen atom (X) in am olecule or moiety,a nd an ucleophilic region (B) in another molecule or moiety.S tructurally,t he electrophilic region at the halogen atom has been associated with a" s hole". In recent times, halogen bondingh as impacted diverse fields including supramolecular chemistry,o rganic synthesis, catalysis, separation chemistry,b iology,e tc. [2] In adducing evidencef or halogen bonding av arietyo ft heoretical studies have been reported, besidese xperimental structural studies in solution and solid state. [3] NMR [4a-m] andE SR [5] investigations are among major experimentalt echniques employed in recent times. In particular, one may mention NMR chemicals hift titration, [4a] heteronuclear Overhauser effect (NOE) measurements, [4g] as well as NMR self-diffusion measurements [4h] on halogen bondedc omplexes. ESR studies have typically involved an itroxide free radicalt hat doubles up as the nucleophile. [5] In our view,m ost such studies reported thus far do not directly establish the motional dynamics of "halogen bonded" species, but principally infer the presence of some form of interaction, for example, either by NMR chemical shift changes or by changes in self-diffusion coefficients measured by NMR. The NMR chemical shift( 1 H/ 19 F) titrationa pproach runs into difficulties when small or negligible chemical shift change is observed, and the stoichiometry of the adduct is unknown.Interpretations of NOE 4g measurements are often vitiated by employing at wo-spin model well beyond its region of approximate validity in am ultispin system, i.e.,b eyond the initial build-up rate regime. NOE'sa lso becomev ery weak on the rotational model if the s...

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“…This review shows how crucial information about halogen bonding adducts can be obtained by advanced NMR techniques. It is proposed that advanced NMR techniques could be used increasingly in the near future in the consolidated, but still fruitful and rapidly evolving, field of halogen bonding in solution [21].…”

Section: F Detection To Fluorinatedmentioning

confidence: 99%

Nuclear Magnetic Resonance Spectroscopy

Lehmann

2018

Magnetochemistry

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Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Cited by 14 publications

References 108 publications

Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Motional Dynamics of Halogen‐Bonded Complexes Probed by Low‐Field NMR Relaxometry and Overhauser Dynamic Nuclear Polarization

Nuclear Magnetic Resonance Spectroscopy

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