Water-Assisted Proton Transfer in the Sequential Hydration of Benzonitrile Radical Cation C6H5CN•+(H2O) n : Transition to Hydrated Distonic Cation •C6H4CNH+(H2O) n with n ≥ 4

The stepwise hydration of the benzonitrile•+ radical cation with one–seven H2O molecules was investigated experimentally and computationally with density functional theory in C6H5CN•+(H2O) n clusters. The stepwise binding energies (ΔH n–1,n °) were determined by equilibrium measurements for C6H5CN•+...

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Veröffentlicht in:Journal of the American Chemical Society 2022-06, Vol.144 (22), p.9684-9694
Hauptverfasser: Mason, Kyle A., Pearcy, Adam C., Christensen, Zachary A., Attah, Isaac K., Meot-Ner (Mautner), Michael, El-Shall, M. Samy
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container_issue 22
container_start_page 9684
container_title Journal of the American Chemical Society
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creator Mason, Kyle A.
Pearcy, Adam C.
Christensen, Zachary A.
Attah, Isaac K.
Meot-Ner (Mautner), Michael
El-Shall, M. Samy
description The stepwise hydration of the benzonitrile•+ radical cation with one–seven H2O molecules was investigated experimentally and computationally with density functional theory in C6H5CN•+(H2O) n clusters. The stepwise binding energies (ΔH n–1,n °) were determined by equilibrium measurements for C6H5CN•+(H2O) and for •C6H4CNH+(H2O) n with n = 5, 6, and 7 to be 8.8 and 11.3, 11.0, and 10.0 kcal/mol, respectively. The populations of n = 2 and 3 of the C6H5CN•+(H2O) n clusters were observed only in trace abundance due to fast depletion processes leading to the formation of the hydrated distonic cations •C6H4CNH+(H2O) n with n = 4–7. The observed transition occurs between conventional radical cations hydrated on the ring in C6H5CN•+(H2O) n clusters with n = 1–3 and the protonated radical •C6H4CNH+ (distonic ion) formed by a proton transfer to the CN nitrogen and ionic hydrogen bonding to water molecules in •C6H4CNH+(H2O) n clusters with n = 4–7. The measured binding energy of the hydrated ion C6H5CN•+(H2O) (8.8 kcal/mol) is similar to that of the hydrated benzene radical cation (8.5 kcal/mol) that involves a relatively weak CHδ+···O hydrogen bonding interaction. Also, the measured binding energies of the •C6H4CNH+(H2O) n clusters with n = 5–7 are similar to those of the protonated benzonitrile (methanol) n clusters [C6H5CNH+(CH3OH) n , n = 5–7] that involve CNH+···O ionic hydrogen bonds. The proton shift from the para-•C ring carbon to the nitrogen of the benzonitrile radical cation is endothermic without solvent but thermoneutral for n = 1 and exothermic for n = 2–4 in C6H5CN•+(H2O) n clusters to form the distonic •C6H4CN···H+(OH2) n clusters. The distonic clusters •C6H4CN···H+(OH2) n constitute a new class of structures in radical ion/solvent clusters.
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Samy</creator><creatorcontrib>Mason, Kyle A. ; Pearcy, Adam C. ; Christensen, Zachary A. ; Attah, Isaac K. ; Meot-Ner (Mautner), Michael ; El-Shall, M. Samy</creatorcontrib><description>The stepwise hydration of the benzonitrile•+ radical cation with one–seven H2O molecules was investigated experimentally and computationally with density functional theory in C6H5CN•+(H2O) n clusters. The stepwise binding energies (ΔH n–1,n °) were determined by equilibrium measurements for C6H5CN•+(H2O) and for •C6H4CNH+(H2O) n with n = 5, 6, and 7 to be 8.8 and 11.3, 11.0, and 10.0 kcal/mol, respectively. The populations of n = 2 and 3 of the C6H5CN•+(H2O) n clusters were observed only in trace abundance due to fast depletion processes leading to the formation of the hydrated distonic cations •C6H4CNH+(H2O) n with n = 4–7. The observed transition occurs between conventional radical cations hydrated on the ring in C6H5CN•+(H2O) n clusters with n = 1–3 and the protonated radical •C6H4CNH+ (distonic ion) formed by a proton transfer to the CN nitrogen and ionic hydrogen bonding to water molecules in •C6H4CNH+(H2O) n clusters with n = 4–7. The measured binding energy of the hydrated ion C6H5CN•+(H2O) (8.8 kcal/mol) is similar to that of the hydrated benzene radical cation (8.5 kcal/mol) that involves a relatively weak CHδ+···O hydrogen bonding interaction. Also, the measured binding energies of the •C6H4CNH+(H2O) n clusters with n = 5–7 are similar to those of the protonated benzonitrile (methanol) n clusters [C6H5CNH+(CH3OH) n , n = 5–7] that involve CNH+···O ionic hydrogen bonds. The proton shift from the para-•C ring carbon to the nitrogen of the benzonitrile radical cation is endothermic without solvent but thermoneutral for n = 1 and exothermic for n = 2–4 in C6H5CN•+(H2O) n clusters to form the distonic •C6H4CN···H+(OH2) n clusters. 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Samy</creatorcontrib><title>Water-Assisted Proton Transfer in the Sequential Hydration of Benzonitrile Radical Cation C6H5CN•+(H2O) n : Transition to Hydrated Distonic Cation •C6H4CNH+(H2O) n with n ≥ 4</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>The stepwise hydration of the benzonitrile•+ radical cation with one–seven H2O molecules was investigated experimentally and computationally with density functional theory in C6H5CN•+(H2O) n clusters. The stepwise binding energies (ΔH n–1,n °) were determined by equilibrium measurements for C6H5CN•+(H2O) and for •C6H4CNH+(H2O) n with n = 5, 6, and 7 to be 8.8 and 11.3, 11.0, and 10.0 kcal/mol, respectively. The populations of n = 2 and 3 of the C6H5CN•+(H2O) n clusters were observed only in trace abundance due to fast depletion processes leading to the formation of the hydrated distonic cations •C6H4CNH+(H2O) n with n = 4–7. The observed transition occurs between conventional radical cations hydrated on the ring in C6H5CN•+(H2O) n clusters with n = 1–3 and the protonated radical •C6H4CNH+ (distonic ion) formed by a proton transfer to the CN nitrogen and ionic hydrogen bonding to water molecules in •C6H4CNH+(H2O) n clusters with n = 4–7. The measured binding energy of the hydrated ion C6H5CN•+(H2O) (8.8 kcal/mol) is similar to that of the hydrated benzene radical cation (8.5 kcal/mol) that involves a relatively weak CHδ+···O hydrogen bonding interaction. Also, the measured binding energies of the •C6H4CNH+(H2O) n clusters with n = 5–7 are similar to those of the protonated benzonitrile (methanol) n clusters [C6H5CNH+(CH3OH) n , n = 5–7] that involve CNH+···O ionic hydrogen bonds. The proton shift from the para-•C ring carbon to the nitrogen of the benzonitrile radical cation is endothermic without solvent but thermoneutral for n = 1 and exothermic for n = 2–4 in C6H5CN•+(H2O) n clusters to form the distonic •C6H4CN···H+(OH2) n clusters. 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Samy</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a151t-594e93edd153f014c33b257f6bd8619e09270934869d5dd744dcbde322348fd43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mason, Kyle A.</creatorcontrib><creatorcontrib>Pearcy, Adam C.</creatorcontrib><creatorcontrib>Christensen, Zachary A.</creatorcontrib><creatorcontrib>Attah, Isaac K.</creatorcontrib><creatorcontrib>Meot-Ner (Mautner), Michael</creatorcontrib><creatorcontrib>El-Shall, M. Samy</creatorcontrib><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mason, Kyle A.</au><au>Pearcy, Adam C.</au><au>Christensen, Zachary A.</au><au>Attah, Isaac K.</au><au>Meot-Ner (Mautner), Michael</au><au>El-Shall, M. Samy</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Water-Assisted Proton Transfer in the Sequential Hydration of Benzonitrile Radical Cation C6H5CN•+(H2O) n : Transition to Hydrated Distonic Cation •C6H4CNH+(H2O) n with n ≥ 4</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2022-06-08</date><risdate>2022</risdate><volume>144</volume><issue>22</issue><spage>9684</spage><epage>9694</epage><pages>9684-9694</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The stepwise hydration of the benzonitrile•+ radical cation with one–seven H2O molecules was investigated experimentally and computationally with density functional theory in C6H5CN•+(H2O) n clusters. The stepwise binding energies (ΔH n–1,n °) were determined by equilibrium measurements for C6H5CN•+(H2O) and for •C6H4CNH+(H2O) n with n = 5, 6, and 7 to be 8.8 and 11.3, 11.0, and 10.0 kcal/mol, respectively. The populations of n = 2 and 3 of the C6H5CN•+(H2O) n clusters were observed only in trace abundance due to fast depletion processes leading to the formation of the hydrated distonic cations •C6H4CNH+(H2O) n with n = 4–7. The observed transition occurs between conventional radical cations hydrated on the ring in C6H5CN•+(H2O) n clusters with n = 1–3 and the protonated radical •C6H4CNH+ (distonic ion) formed by a proton transfer to the CN nitrogen and ionic hydrogen bonding to water molecules in •C6H4CNH+(H2O) n clusters with n = 4–7. The measured binding energy of the hydrated ion C6H5CN•+(H2O) (8.8 kcal/mol) is similar to that of the hydrated benzene radical cation (8.5 kcal/mol) that involves a relatively weak CHδ+···O hydrogen bonding interaction. Also, the measured binding energies of the •C6H4CNH+(H2O) n clusters with n = 5–7 are similar to those of the protonated benzonitrile (methanol) n clusters [C6H5CNH+(CH3OH) n , n = 5–7] that involve CNH+···O ionic hydrogen bonds. The proton shift from the para-•C ring carbon to the nitrogen of the benzonitrile radical cation is endothermic without solvent but thermoneutral for n = 1 and exothermic for n = 2–4 in C6H5CN•+(H2O) n clusters to form the distonic •C6H4CN···H+(OH2) n clusters. The distonic clusters •C6H4CN···H+(OH2) n constitute a new class of structures in radical ion/solvent clusters.</abstract><pub>American Chemical Society</pub><doi>10.1021/jacs.2c01143</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-1013-4948</orcidid></addata></record>
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title Water-Assisted Proton Transfer in the Sequential Hydration of Benzonitrile Radical Cation C6H5CN•+(H2O) n : Transition to Hydrated Distonic Cation •C6H4CNH+(H2O) n with n ≥ 4
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