{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,17]],"date-time":"2026-07-17T22:42:17Z","timestamp":1784328137826,"version":"3.55.0"},"reference-count":39,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2013,11,20]],"date-time":"2013-11-20T00:00:00Z","timestamp":1384905600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2014,1,13]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The C\uf8ffH\u22c5\u22c5\u22c5Y (Y=hydrogen\u2010bond acceptor) interactions are somewhat unconventional in the context of hydrogen\u2010bonding interactions. Typical C\uf8ffH stretching frequency shifts in the hydrogen\u2010bond donor C\uf8ffH group are not only small, that is, of the order of a few tens of cm<jats:sup>\u22121<\/jats:sup>, but also bidirectional, that is, they can be red or blue shifted depending on the hydrogen\u2010bond acceptor. In this work we examine the C\uf8ffH\u22c5\u22c5\u22c5N interaction in complexes of 7\u2010azaindole with CHCl<jats:sub>3<\/jats:sub> and CHF<jats:sub>3<\/jats:sub> that are prepared in the gas phase through supersonic jet expansion using the fluorescence depletion by infra\u2010red (FDIR) method. Although the hydrogen\u2010bond acceptor, 7\u2010azaindole, has multiple sites of interaction, it is found that the C\uf8ffH\u22c5\u22c5\u22c5N hydrogen\u2010bonding interaction prevails over the others. The electronic excitation spectra suggest that both complexes are more stabilized in the S<jats:sub>1<\/jats:sub> state than in the S<jats:sub>0<\/jats:sub> state. The C\uf8ffH stretching frequency is found to be red shifted by 82 cm<jats:sup>\u22121<\/jats:sup> in the CHCl<jats:sub>3<\/jats:sub> complex, which is the largest redshift reported so far in gas\u2010phase investigations of 1:1 haloform complexes with various substrates. In the CHF<jats:sub>3<\/jats:sub> complex the observed C\uf8ffH frequency is blue shifted by 4 cm<jats:sup>\u22121<\/jats:sup>. This is at variance with the frequency shifts that are predicted using several computational methods; these predict at best a redshift of 8.5 cm<jats:sup>\u22121<\/jats:sup>. This discrepancy is analogous to that reported for the pyridine\u2010CHF<jats:sub>3<\/jats:sub> complex [W. A. Herrebout, S. M. Melikova, S. N. Delanoye, K. S. Rutkowski, D. N. Shchepkin, B. J. van der Veken, <jats:italic>J. Phys. Chem. A<\/jats:italic>\u00ad <jats:bold>2005<\/jats:bold>, <jats:italic>109<\/jats:italic>, 3038], in which the blueshift is termed a pseudo blueshift and is shown to be due to the shifting of levels caused by Fermi resonance between the overtones of the C\uf8ffH bending and stretching modes. The dissociation energies, (<jats:italic>D<\/jats:italic><jats:sub>0<\/jats:sub>), of the CHCl<jats:sub>3<\/jats:sub> and CHF<jats:sub>3<\/jats:sub> complexes are computed (MP2\/aug\u2010cc\u2010pVDZ level) as 6.46 and 5.06 kcal\u2009mol<jats:sup>\u22121<\/jats:sup>, respectively.<\/jats:p>","DOI":"10.1002\/cphc.201300731","type":"journal-article","created":{"date-parts":[[2013,11,20]],"date-time":"2013-11-20T06:56:46Z","timestamp":1384930606000},"page":"109-117","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["C\uf8ffH\u22c5\u22c5\u22c5N Hydrogen\u2010Bonding Interaction in 7\u2010Azaindole:CHX<sub>3<\/sub> (X=F, Cl) Complexes"],"prefix":"10.1002","volume":"15","author":[{"given":"Pranav R.","family":"Shirhatti","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dilip K.","family":"Maity","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Surjendu","family":"Bhattacharyya","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sanjay","family":"Wategaonkar","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2013,11,20]]},"reference":[{"key":"e_1_2_5_1_2","volume-title":"The Weak Hydrogen Bond in Structural Chemistry and Biology","author":"Desiraju G. 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