2014
DOI: 10.1007/128_2014_559
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Infrared and Raman Measurements of Halogen Bonding in Cryogenic Solutions

Abstract: Because they create a weakly interacting environment which, combined with the low temperatures used, leads to small bandwidths and thus facilitates the detection of complex bands only slightly shifted from the monomer modes, solutions in liquefied inert gases have proven to be an ideal medium to study molecular complexes held together by weak and medium-strong C-X…Y (with X=I, Br, Cl and Y=O, N, S, F, Cl, π,…) halogen bonds. In this chapter, experimental setups for infrared and Raman study of cryosolutions are… Show more

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Cited by 21 publications
(21 citation statements)
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“…As the experimental setup does not allow for verification of full solubility of the compounds, or verification of the fluid level in the filling tube, only approximate concentrations are known. 14 Experimental complexation enthalpies were determined by using the van 't Hoff isochore, based on measurements performed in the 120−156 K temperature interval. Using a subtraction procedure in which spectra of monomer solutions, recorded at identical temperatures and similar concentrations, are rescaled and subtracted from the spectrum of the mixture, a spectrum containing solely complex bands is obtained in the first phase of the actual analysis.…”
Section: Methodsmentioning
confidence: 99%
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“…As the experimental setup does not allow for verification of full solubility of the compounds, or verification of the fluid level in the filling tube, only approximate concentrations are known. 14 Experimental complexation enthalpies were determined by using the van 't Hoff isochore, based on measurements performed in the 120−156 K temperature interval. Using a subtraction procedure in which spectra of monomer solutions, recorded at identical temperatures and similar concentrations, are rescaled and subtracted from the spectrum of the mixture, a spectrum containing solely complex bands is obtained in the first phase of the actual analysis.…”
Section: Methodsmentioning
confidence: 99%
“…Using a subtraction procedure in which spectra of monomer solutions, recorded at identical temperatures and similar concentrations, are rescaled and subtracted from the spectrum of the mixture, a spectrum containing solely complex bands is obtained in the first phase of the actual analysis. 14 Subsequently band intensities of monomers and complexes are integrated numerically, or, for cases for which both complex bands are not fully resolved, are obtained from band fit analyses. Thermal expansion of the solvent gas during temperature studies was accounted for using the method published by van der Veken.…”
Section: Methodsmentioning
confidence: 99%
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“…By performing measurements at variable temperature, the complexation enthalpy could also be determined from the van’t Hoff plot of the logarithm of the complex:monomer intensity ratio versus the inverse of the temperature, according to the following equation: 417 where a and b are temperature-independent constants which define the dependency of the cryosolvent density on the temperature and R is the ideal gas constant.…”
Section: Nature Of the Halogen Bondmentioning
confidence: 99%
“…Halogen bonds should be able to stabilize the singlet state S- 6 in a similar way as hydrogen bonds, and we therefore investigated the reaction of carbene 6 with CF 3 I and CF 3 Br as halogen bond donors. These donors were selected since they have been shown to form strong halogen bonds with various Lewis bases, and in addition are small enough to diffuse in solid argon during annealing. Thus, warming a CF 3 I-doped argon matrix from 8 to 25 K results in the formation of van der Waals dimers .…”
Section: Introductionmentioning
confidence: 99%