{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T13:31:13Z","timestamp":1780666273552,"version":"3.54.1"},"reference-count":39,"publisher":"MDPI AG","issue":"6","license":[{"start":{"date-parts":[[2013,6,10]],"date-time":"2013-06-10T00:00:00Z","timestamp":1370822400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/3.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The formation of halogen bonded complexes formed between the trifluorohalomethanes CF3Cl, CF3Br and CF3I and the Lewis bases benzene and toluene at temperatures below 150K was investigated using FTIR and Raman spectroscopy. Experiments using liquid krypton as solvent show that for both CF3Br and CF3I substantial fractions of the monomers can be involved in 1:1 complexes. In addition, weak absorptions illustrating the formation of 2:1 complexes between CF3I and benzene are observed. Using spectra recorded at temperatures between 120 and 140 K, observed information on the relative stability was obtained for all complexes by determining the complexation enthalpies in solution. The resulting values for CF3Br.benzene, CF3I.benzene and (CF3I)2.benzene are \u22126.5(3), \u22127.6(2) and \u221214.5(9) kJ mol\u22121. The values for CF3Br.toluene and CF3I.toluene are \u22126.2(5) and \u22127.4(5) kJ mol\u22121. The experimental complexation enthalpies are compared with theoretical data obtained by combining results from MP2\/aug-cc-pVDZ(-PP) and MP2\/aug-cc-pVTZ(-PP) ab initio calculations, from statistical thermodynamical calculations and from Monte Carlo Free Energy Perturbation simulations. The data are also compared with results derived for other C-X\u00b7\u00b7\u00b7\u03c0 halogen bonded complexes involving unsaturated Lewis bases such as ethene and ethyne.<\/jats:p>","DOI":"10.3390\/molecules18066829","type":"journal-article","created":{"date-parts":[[2013,6,10]],"date-time":"2013-06-10T11:17:56Z","timestamp":1370863076000},"page":"6829-6851","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":55,"title":["Exploring the C-X\u2026\u03c0 Halogen Bonding Motif: An Infrared and Raman Study of the Complexes of CF3X (X = Cl, Br and I) with the Aromatic Model Compounds Benzene and Toluene"],"prefix":"10.3390","volume":"18","author":[{"given":"Nick","family":"Nagels","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dieter","family":"Hauchecorne","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wouter","family":"Herrebout","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2013,6,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"6114","DOI":"10.1002\/anie.200800128","article-title":"Halogen bonding in supramolecular chemistry","volume":"47","author":"Metrangolo","year":"2008","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3058","DOI":"10.1039\/C2CE26150B","article-title":"Halogen bonding at work: Recent applications in synthetic chemistry and materials science","volume":"15","author":"Meyer","year":"2013","journal-title":"CrystEngComm"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1002\/pro.2201","article-title":"Halogen bonding: A biological perspective","volume":"22","author":"Scholfield","year":"2013","journal-title":"Protein Sci."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4543","DOI":"10.1039\/b926326h","article-title":"Nonbonding interactions of organic halogens in biological systems: implications for drug discovery and biomolecular design","volume":"12","author":"Lu","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1363","DOI":"10.1021\/jm3012068","article-title":"Principles and applications of halogen bonding in medicinal chemistry and chemical biology","volume":"56","author":"Wilcken","year":"2013","journal-title":"J. Med. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"5027","DOI":"10.1039\/c2ce25338k","article-title":"Phosphorescent cocrystals constructed by 1,4-diiodotetrafluorobenzene and polyaromatic hydrocarbons based on C\u2013I\u2026\u03c0 halogen bonding and other assisting weak interactions","volume":"14","author":"Shen","year":"2012","journal-title":"CrystEngComm"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2722","DOI":"10.1039\/c3ce26661c","article-title":"Co-crystallization turned on the phosphorescence of phenanthrene by C-Br center dot center dot center dot pi halogen bonding, pi-hole center dot center dot center dot pi bonding and other assisting interactions","volume":"15","author":"Pang","year":"2013","journal-title":"CrystEngComm"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5336","DOI":"10.1039\/c2jm16257a","article-title":"Phosphorescent co-crystal assembled by 1,4-diiodotetrafluorobenzene with carbazole based on C-I center dot center dot center dot pi halogen bonding","volume":"22","author":"Gao","year":"2012","journal-title":"J. Mater. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1016\/j.chemphys.2010.12.012","article-title":"A 19F NMR study of C-I\u22ef\u03c0 halogen bonding","volume":"381","author":"Hauchecorne","year":"2011","journal-title":"Chem. Phys."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2105","DOI":"10.1002\/cphc.200900125","article-title":"C-X\u22c5\u22c5\u22c5O halogen bonding: interactions of trifluoromethyl halides with dimethyl ether","volume":"10","author":"Hauchecorne","year":"2009","journal-title":"Chemphyschem"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"30","DOI":"10.1016\/j.chemphys.2010.06.004","article-title":"The C-Cl\u00e2\u22ef\u00afN halogen bond, the weaker relative of the C-I and C-Br\u22efN halogen bonds, finally characterized in solution","volume":"374","author":"Hauchecorne","year":"2010","journal-title":"Chem. Phys."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"10204","DOI":"10.1039\/c0cp02960b","article-title":"Halogen bonding to a divalent sulfur atom: an experimental study of the interactions of CF3X (X = Cl, Br, I) with dimethyl sulfide","volume":"13","author":"Hauchecorne","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"681","DOI":"10.1039\/C1CP22771H","article-title":"C-X\u00b7\u00b7\u00b7\u03c0 halogen and C-H\u00b7\u00b7\u00b7\u03c0 hydrogen bonding: interactions of CF3X (X = Cl, Br, I or H) with ethene and propene","volume":"14","author":"Hauchecorne","year":"2012","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.cplett.2008.04.106","article-title":"Evaluation of true energy of halogen bonding in the crystals of halogen derivatives of trityl alcohol","volume":"458","author":"Shishkin","year":"2008","journal-title":"Chem. Phys. Lett."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chemphys.2006.12.011","article-title":"Theoretical investigations of the C-X\u00b7\u00b7\u00b7\u03c0 interactions between benzene and some model halocarbons","volume":"334","author":"Lu","year":"2007","journal-title":"Chem. Phys."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2295","DOI":"10.1039\/a803873b","article-title":"Interaction of benzene and halogens in the gas-phase: rotational spectrum of C6H6\u00b7\u00b7\u00b7ClF","volume":"94","author":"Cooke","year":"1998","journal-title":"J. Chem. Soc. Faraday Trans."},{"key":"ref_17","unstructured":"Legon, A.C. (2008). The Interaction of Dihalogens and Hydrogen Halides with Lewis Bases in the Gas Phase: An Experimental Comparison of the Halogen Bond and the Hydrogen Bond, Springer."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1007\/s00894-006-0130-2","article-title":"Halogen bonding: the \u03c3-hole","volume":"13","author":"Clark","year":"2007","journal-title":"J. Mol. Model."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.molstruc.2005.04.018","article-title":"Infrared intensities of liquids XXV: Dielectric constants, molar polarizabilities and integrated intensities of liquid toluene at 25 \u00b0C between 4800 and 400 cm\u22121","volume":"750","author":"Bertie","year":"2005","journal-title":"J. Mol. Struct."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"14034","DOI":"10.1039\/c0cp00771d","article-title":"The complexes of halothane with benzene: the temperature dependent direction of the complexation shift of the aliphatic C\u2013H stretching","volume":"12","author":"Michielsen","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"14142","DOI":"10.1039\/c1cp20693a","article-title":"On the weakly C-H\u00b7\u00b7\u00b7\u03c0 hydrogen bonded complexes of sevoflurane and benzene","volume":"13","author":"Dom","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"231101","DOI":"10.1063\/1.3442466","article-title":"Communications: Intramolecular basis set superposition error as a measure of basis set incompleteness: Can one reach the basis set limit without extrapolation?","volume":"132","author":"Balabin","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1047","DOI":"10.1007\/s11224-011-9793-0","article-title":"On the relation between basis set convergence and electron correlation: a critical test for modern ab initio quantum chemistry on a \u201cmindless\u201d data set","volume":"22","author":"Balabin","year":"2011","journal-title":"Struct. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"13855","DOI":"10.1021\/jp035839q","article-title":"Direct measurement of the stability of the supramolecular synthon C6H6\u00b7C6F6","volume":"107","author":"Vanspeybrouck","year":"2003","journal-title":"J. Phys. Chem. B"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"956","DOI":"10.1016\/j.ccr.2012.10.013","article-title":"Main group coordination chemistry at low temperatures: A review of matrix isolated Group 12 to Group 18 complexes","volume":"257","author":"Young","year":"2013","journal-title":"Coord. Chem. Rev."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"17436","DOI":"10.1021\/jp9617478","article-title":"Measurement of enthalpy differences in cryosolutions:\u2009 Influence of thermal expansion","volume":"100","year":"1996","journal-title":"J. Phys. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"330","DOI":"10.1021\/ct300842d","article-title":"Basis set dependence of interaction energies computed using composite Post-MP2 methods","volume":"9","author":"Platts","year":"2013","journal-title":"J. Chem. Theory Comput."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"4285","DOI":"10.1021\/ct300647k","article-title":"Benchmark calculations of noncovalent interactions of halogenated molecules","volume":"8","author":"Rezac","year":"2012","journal-title":"J. Chem. Theory Comput."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"4159","DOI":"10.1021\/jp211997b","article-title":"Assessment of the performance of MP2 and MP2 variants for the treatment of noncovalent interactions","volume":"116","author":"Riley","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"698","DOI":"10.1002\/cphc.201200850","article-title":"MP2.5 and MP2.X: approaching CCSD(T) quality description of noncovalent interaction at the cost of a single CCSD iteration","volume":"14","author":"Sedlak","year":"2013","journal-title":"ChemPhysChem"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"85","DOI":"10.1016\/j.cplett.2008.12.038","article-title":"The C-H\u00b7\u00b7\u00b7\u03c0 interaction in the halothane\/ethene complex: A cryosolution infrared and raman study","volume":"469","author":"Dom","year":"2009","journal-title":"Chem. Phys. Lett."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1188","DOI":"10.1002\/cphc.200700126","article-title":"Intermolecular interactions between halothane and dimethyl ether: A cryosolution infrared and ab initio study","volume":"8","author":"Michielsen","year":"2007","journal-title":"Chemphyschem"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"3054","DOI":"10.1002\/cphc.200900414","article-title":"On the \u03bd1(CO2)\/2\u2009\u03bd2(CO2) Resonance in the Complex of Carbon Dioxide with Dimethyl Ether","volume":"10","author":"Herrebout","year":"2009","journal-title":"ChemPhysChem"},{"key":"ref_34","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Gaussian 09, Gaussian, Inc.. Revision B.01."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"553","DOI":"10.1080\/00268977000101561","article-title":"The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors","volume":"19","author":"Boys","year":"1970","journal-title":"Mol. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"11024","DOI":"10.1063\/1.472902","article-title":"How does basis set superposition error change the potential surfaces for hydrogen\u2010bonded dimers?","volume":"105","author":"Simon","year":"1996","journal-title":"J. Chem. Phys."},{"key":"ref_37","unstructured":"EMSL basis set library. Available online: https:\/\/bse.pnl.gov\/bse\/portal\/."},{"key":"ref_38","unstructured":"Knox, J.H. (1971). Molecular Thermodynamics: An Introduction to Statistical Mechanics for Chemists, Wiley-Interscience."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"9836","DOI":"10.1021\/jp051476d","article-title":"Stabilities of the C-H\u00b7\u00b7\u00b7O bonded complexes of the haloforms HCClnF3-n (n = 0\u20133) with dimethyl ether, oxirane, and acetone: An experimental and theoretical study","volume":"109","author":"Delanoye","year":"2005","journal-title":"J. Phys. Chem. A"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/18\/6\/6829\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T21:47:17Z","timestamp":1760219237000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/18\/6\/6829"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2013,6,10]]},"references-count":39,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2013,6]]}},"alternative-id":["molecules18066829"],"URL":"https:\/\/doi.org\/10.3390\/molecules18066829","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2013,6,10]]}}}