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Structures of benzonitrile dimer radical cation and the protonated dimer: Observation of hydronium ion core solvated by benzonitrile molecules.
J Chem Phys. 2019 Mar 28; 150(12):124303.JC

Abstract

The recent discovery of benzonitrile (C6H5CN), one of the simplest nitrogen-bearing polar aromatic molecules, in the interstellar medium motivates structural characterization of the benzonitrile-containing molecular ions as potential precursors for nitrogen-containing complex organics in space. Herein, we present mass-selected ion mobility measurements combined with density functional theory (DFT) calculations to reveal, for the first time, the structures of the benzonitrile dimer radical cation, the protonated dimer, and the protonated hydrated small clusters in the gas phase. The measured collision cross sections of the investigated ions in helium are in excellent agreement with the calculated values of the lowest energy DFT structures. Unlike the dimer radical cations of nonpolar aromatic molecules which adopt parallel sandwich configurations, the (C6H5CN)2 ·+ displays a symmetrically planar geometry with a double hydrogen bond formed between the nitrogen and hydrogen atoms. The protonated dimer has the structure of a proton-bound dimer (C6H5CNH+NCC6H5) where the bridging proton connects the nitrogen atoms in the two benzonitrile molecules resulting in a calculated collision cross section of 101.1 Å2 in excellent agreement with the measured value of 103.3 Å2. The structure of the hydrated protonated trimer consists of a hydronium ion core solvated by three benzonitrile molecules. By locating the proton on the lower proton affinity water molecule, the resulting hydronium ion can be fully solvated by forming three ionic hydrogen bonds with the benzonitrile molecules. These unique structural motifs could be useful for the molecular design and recognition involving charged aromatic systems and also for the search of nitrogen-containing complex organics in space.

Authors+Show Affiliations

Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, USA.Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, USA.Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, USA.Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, USA.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

30927904

Citation

Mason, Kyle A., et al. "Structures of Benzonitrile Dimer Radical Cation and the Protonated Dimer: Observation of Hydronium Ion Core Solvated By Benzonitrile Molecules." The Journal of Chemical Physics, vol. 150, no. 12, 2019, p. 124303.
Mason KA, Pearcy AC, Hamid AM, et al. Structures of benzonitrile dimer radical cation and the protonated dimer: Observation of hydronium ion core solvated by benzonitrile molecules. J Chem Phys. 2019;150(12):124303.
Mason, K. A., Pearcy, A. C., Hamid, A. M., & El-Shall, M. S. (2019). Structures of benzonitrile dimer radical cation and the protonated dimer: Observation of hydronium ion core solvated by benzonitrile molecules. The Journal of Chemical Physics, 150(12), 124303. https://doi.org/10.1063/1.5094648
Mason KA, et al. Structures of Benzonitrile Dimer Radical Cation and the Protonated Dimer: Observation of Hydronium Ion Core Solvated By Benzonitrile Molecules. J Chem Phys. 2019 Mar 28;150(12):124303. PubMed PMID: 30927904.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Structures of benzonitrile dimer radical cation and the protonated dimer: Observation of hydronium ion core solvated by benzonitrile molecules. AU - Mason,Kyle A, AU - Pearcy,Adam C, AU - Hamid,Ahmed M, AU - El-Shall,M Samy, PY - 2019/4/1/entrez PY - 2019/4/1/pubmed PY - 2019/4/1/medline SP - 124303 EP - 124303 JF - The Journal of chemical physics JO - J Chem Phys VL - 150 IS - 12 N2 - The recent discovery of benzonitrile (C6H5CN), one of the simplest nitrogen-bearing polar aromatic molecules, in the interstellar medium motivates structural characterization of the benzonitrile-containing molecular ions as potential precursors for nitrogen-containing complex organics in space. Herein, we present mass-selected ion mobility measurements combined with density functional theory (DFT) calculations to reveal, for the first time, the structures of the benzonitrile dimer radical cation, the protonated dimer, and the protonated hydrated small clusters in the gas phase. The measured collision cross sections of the investigated ions in helium are in excellent agreement with the calculated values of the lowest energy DFT structures. Unlike the dimer radical cations of nonpolar aromatic molecules which adopt parallel sandwich configurations, the (C6H5CN)2 ·+ displays a symmetrically planar geometry with a double hydrogen bond formed between the nitrogen and hydrogen atoms. The protonated dimer has the structure of a proton-bound dimer (C6H5CNH+NCC6H5) where the bridging proton connects the nitrogen atoms in the two benzonitrile molecules resulting in a calculated collision cross section of 101.1 Å2 in excellent agreement with the measured value of 103.3 Å2. The structure of the hydrated protonated trimer consists of a hydronium ion core solvated by three benzonitrile molecules. By locating the proton on the lower proton affinity water molecule, the resulting hydronium ion can be fully solvated by forming three ionic hydrogen bonds with the benzonitrile molecules. These unique structural motifs could be useful for the molecular design and recognition involving charged aromatic systems and also for the search of nitrogen-containing complex organics in space. SN - 1089-7690 UR - https://www.unboundmedicine.com/medline/citation/30927904/Structures_of_benzonitrile_dimer_radical_cation_and_the_protonated_dimer:_Observation_of_hydronium_ion_core_solvated_by_benzonitrile_molecules L2 - https://dx.doi.org/10.1063/1.5094648 DB - PRIME DP - Unbound Medicine ER -
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