Preparation and Characterization of the Halogen-Bonding Motif in the Isolated Cl–·IOH Complex with Cryogenic Ion Vibrational SpectroscopyClick to copy article linkArticle link copied!
- Santino J. StropoliSantino J. StropoliSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Santino J. Stropoli
- Thien KhuuThien KhuuSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Thien Khuu
- Joseph P. MessingerJoseph P. MessingerSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Joseph P. Messinger
- Natalia V. KarimovaNatalia V. KarimovaDepartment of Chemistry, University of California, Irvine, Irvine, California 92697, United StatesMore by Natalia V. Karimova
- Mark A. BoyerMark A. BoyerDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Mark A. Boyer
- Itai ZakaiItai ZakaiInstitute of Chemistry and the Fritz-Haber Center for Molecular Dynamics, The Hebrew University, Jerusalem 91905, IsraelMore by Itai Zakai
- Sayoni MitraSayoni MitraSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Sayoni Mitra
- Anton L. LachowiczAnton L. LachowiczSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Anton L. Lachowicz
- Nan YangNan YangSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Nan Yang
- Sean C. EdingtonSean C. EdingtonSterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Sean C. Edington
- R. Benny Gerber*R. Benny Gerber*Email: [email protected]Department of Chemistry, University of California, Irvine, Irvine, California 92697, United StatesInstitute of Chemistry and the Fritz-Haber Center for Molecular Dynamics, The Hebrew University, Jerusalem 91905, IsraelMore by R. Benny Gerber
- Anne B. McCoy*Anne B. McCoy*Email: [email protected]Department of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Anne B. McCoy
- Mark A. Johnson*Mark A. Johnson*Email: [email protected]Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520, United StatesMore by Mark A. Johnson
Abstract

In the presence of a halide ion, hypohalous acids can adopt two binding motifs upon formation of the ion–molecule complexes [XHOY]− (X, Y = Cl, Br, I): a hydrogen (HB) bond to the acid OH group and a halogen (XB) bond between the anion and the acid halogen. Here we isolate the X-bonded Cl–·IOH ion–molecule complex by collisions of I–·(H2O)n clusters with HOCl vapor and measure its vibrational spectrum by IR photodissociation of the H2-tagged complex. Anharmonic analysis of its vibrational band pattern reveals that formation of the XB complex results in dramatic lowering of the HOI bending fundamental frequency and elongation of the O–I bond (by 168 cm–1 and 0.13 Å, respectively, relative to isolated HOI). The frequency of the O–I stretch (estimated 436 cm–1) is also encoded in the spectrum by the weak v = 0 → 2 overtone transition at 872 cm–1.
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