Low barrier hydrogen bond in protonated proton sponge. X-ray diffraction, infrared, and theoretical ab initio and density functional theory studies
A new proton sponge, 2,7-dibromo-1,8-bis(dimethylamino)naphthalene (Br2DMAN), and its protonated (HBr) or deuterated (DBr) forms were studied by using x-ray diffraction and infrared spectroscopy, as well as ab initio and density functional theory calculations. In the crystalline lattice of the Br2DM...
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Veröffentlicht in: | The Journal of chemical physics 2003-08, Vol.119 (8), p.4313-4319 |
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creator | Bieńko, Agnieszka J. Latajka, Zdzisław Sawka-Dobrowolska, Wanda Sobczyk, Lucjan Ozeryanskii, Valery A. Pozharskii, Alexander F. Grech, Eugeniusz Nowicka-Scheibe, Joanna |
description | A new proton sponge, 2,7-dibromo-1,8-bis(dimethylamino)naphthalene (Br2DMAN), and its protonated (HBr) or deuterated (DBr) forms were studied by using x-ray diffraction and infrared spectroscopy, as well as ab initio and density functional theory calculations. In the crystalline lattice of the Br2DMAN.HBr salt, symmetrical (NHN)+ hydrogen bonding of length 2.547(3) Å is observed. No deuterium geometrical isotope effect was detected. The structure refinement suggests disordering of protons between two equivalent positions at the nitrogen atoms. These findings are in agreement with infrared spectra, which are characterized by an intense band centered at ∼560 cm−1 assigned to the ν(NHN) protonic transition. Deuteration leads to a shift of this band to ∼340 cm−1, so that the isotopic ratio νH/νD (ISR) of 1.65 is characteristic of an unusual potential for the proton motion. The results of MP2 calculations are in fairly good agreement with the experimental data. The theoretical N…N hydrogen bond length is 2.575 Å, while the distance between the minima equals to ca. 0.5 Å with a barrier height of 0.70 kcal/mol. The calculated difference between the 0→1 proton (deuteron) levels is 509 (284) cm−1, giving an ISR value of 1.76. |
doi_str_mv | 10.1063/1.1594171 |
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X-ray diffraction, infrared, and theoretical ab initio and density functional theory studies</title><source>AIP Journals Complete</source><source>AIP Digital Archive</source><creator>Bieńko, Agnieszka J. ; Latajka, Zdzisław ; Sawka-Dobrowolska, Wanda ; Sobczyk, Lucjan ; Ozeryanskii, Valery A. ; Pozharskii, Alexander F. ; Grech, Eugeniusz ; Nowicka-Scheibe, Joanna</creator><creatorcontrib>Bieńko, Agnieszka J. ; Latajka, Zdzisław ; Sawka-Dobrowolska, Wanda ; Sobczyk, Lucjan ; Ozeryanskii, Valery A. ; Pozharskii, Alexander F. ; Grech, Eugeniusz ; Nowicka-Scheibe, Joanna</creatorcontrib><description>A new proton sponge, 2,7-dibromo-1,8-bis(dimethylamino)naphthalene (Br2DMAN), and its protonated (HBr) or deuterated (DBr) forms were studied by using x-ray diffraction and infrared spectroscopy, as well as ab initio and density functional theory calculations. In the crystalline lattice of the Br2DMAN.HBr salt, symmetrical (NHN)+ hydrogen bonding of length 2.547(3) Å is observed. No deuterium geometrical isotope effect was detected. The structure refinement suggests disordering of protons between two equivalent positions at the nitrogen atoms. These findings are in agreement with infrared spectra, which are characterized by an intense band centered at ∼560 cm−1 assigned to the ν(NHN) protonic transition. Deuteration leads to a shift of this band to ∼340 cm−1, so that the isotopic ratio νH/νD (ISR) of 1.65 is characteristic of an unusual potential for the proton motion. The results of MP2 calculations are in fairly good agreement with the experimental data. The theoretical N…N hydrogen bond length is 2.575 Å, while the distance between the minima equals to ca. 0.5 Å with a barrier height of 0.70 kcal/mol. The calculated difference between the 0→1 proton (deuteron) levels is 509 (284) cm−1, giving an ISR value of 1.76.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.1594171</identifier><language>eng</language><ispartof>The Journal of chemical physics, 2003-08, Vol.119 (8), p.4313-4319</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c227t-fb811a9d9f875ef8c24e3186babd6f70440c9de18ca2a741e7aa58c93741b2763</citedby><cites>FETCH-LOGICAL-c227t-fb811a9d9f875ef8c24e3186babd6f70440c9de18ca2a741e7aa58c93741b2763</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Bieńko, Agnieszka J.</creatorcontrib><creatorcontrib>Latajka, Zdzisław</creatorcontrib><creatorcontrib>Sawka-Dobrowolska, Wanda</creatorcontrib><creatorcontrib>Sobczyk, Lucjan</creatorcontrib><creatorcontrib>Ozeryanskii, Valery A.</creatorcontrib><creatorcontrib>Pozharskii, Alexander F.</creatorcontrib><creatorcontrib>Grech, Eugeniusz</creatorcontrib><creatorcontrib>Nowicka-Scheibe, Joanna</creatorcontrib><title>Low barrier hydrogen bond in protonated proton sponge. X-ray diffraction, infrared, and theoretical ab initio and density functional theory studies</title><title>The Journal of chemical physics</title><description>A new proton sponge, 2,7-dibromo-1,8-bis(dimethylamino)naphthalene (Br2DMAN), and its protonated (HBr) or deuterated (DBr) forms were studied by using x-ray diffraction and infrared spectroscopy, as well as ab initio and density functional theory calculations. In the crystalline lattice of the Br2DMAN.HBr salt, symmetrical (NHN)+ hydrogen bonding of length 2.547(3) Å is observed. No deuterium geometrical isotope effect was detected. The structure refinement suggests disordering of protons between two equivalent positions at the nitrogen atoms. These findings are in agreement with infrared spectra, which are characterized by an intense band centered at ∼560 cm−1 assigned to the ν(NHN) protonic transition. Deuteration leads to a shift of this band to ∼340 cm−1, so that the isotopic ratio νH/νD (ISR) of 1.65 is characteristic of an unusual potential for the proton motion. The results of MP2 calculations are in fairly good agreement with the experimental data. The theoretical N…N hydrogen bond length is 2.575 Å, while the distance between the minima equals to ca. 0.5 Å with a barrier height of 0.70 kcal/mol. The calculated difference between the 0→1 proton (deuteron) levels is 509 (284) cm−1, giving an ISR value of 1.76.</description><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNotkMFKAzEURYMoWKsL_yBboVPzZqaTyVKKVqHgRsHd8CZ5aSM1KUmKzHf4w461q3fgnvsWl7FbEHMQTXUPc1ioGiScsQmIVhWyUeKcTYQooVCNaC7ZVUqfQgiQZT1hP-vwzXuM0VHk28HEsCHP--ANd57vY8jBYyZzQp72wW9ozj-KiAM3ztqIOrvgZ6M_ciQz4zi285ZCpOw07jj2Y-hG65gY8snlgduDPzZH4SgPPOWDcZSu2YXFXaKb052y96fHt-VzsX5dvSwf1oUuS5kL27cAqIyyrVyQbXVZUwVt02NvGitFXQutDEGrsURZA0nERatVNXJfyqaasrv_vzqGlCLZbh_dF8ahA9H9rdlBd1qz-gVxumpv</recordid><startdate>20030822</startdate><enddate>20030822</enddate><creator>Bieńko, Agnieszka J.</creator><creator>Latajka, Zdzisław</creator><creator>Sawka-Dobrowolska, Wanda</creator><creator>Sobczyk, Lucjan</creator><creator>Ozeryanskii, Valery A.</creator><creator>Pozharskii, Alexander F.</creator><creator>Grech, Eugeniusz</creator><creator>Nowicka-Scheibe, Joanna</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20030822</creationdate><title>Low barrier hydrogen bond in protonated proton sponge. X-ray diffraction, infrared, and theoretical ab initio and density functional theory studies</title><author>Bieńko, Agnieszka J. ; Latajka, Zdzisław ; Sawka-Dobrowolska, Wanda ; Sobczyk, Lucjan ; Ozeryanskii, Valery A. ; Pozharskii, Alexander F. ; Grech, Eugeniusz ; Nowicka-Scheibe, Joanna</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c227t-fb811a9d9f875ef8c24e3186babd6f70440c9de18ca2a741e7aa58c93741b2763</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bieńko, Agnieszka J.</creatorcontrib><creatorcontrib>Latajka, Zdzisław</creatorcontrib><creatorcontrib>Sawka-Dobrowolska, Wanda</creatorcontrib><creatorcontrib>Sobczyk, Lucjan</creatorcontrib><creatorcontrib>Ozeryanskii, Valery A.</creatorcontrib><creatorcontrib>Pozharskii, Alexander F.</creatorcontrib><creatorcontrib>Grech, Eugeniusz</creatorcontrib><creatorcontrib>Nowicka-Scheibe, Joanna</creatorcontrib><collection>CrossRef</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bieńko, Agnieszka J.</au><au>Latajka, Zdzisław</au><au>Sawka-Dobrowolska, Wanda</au><au>Sobczyk, Lucjan</au><au>Ozeryanskii, Valery A.</au><au>Pozharskii, Alexander F.</au><au>Grech, Eugeniusz</au><au>Nowicka-Scheibe, Joanna</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Low barrier hydrogen bond in protonated proton sponge. X-ray diffraction, infrared, and theoretical ab initio and density functional theory studies</atitle><jtitle>The Journal of chemical physics</jtitle><date>2003-08-22</date><risdate>2003</risdate><volume>119</volume><issue>8</issue><spage>4313</spage><epage>4319</epage><pages>4313-4319</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><abstract>A new proton sponge, 2,7-dibromo-1,8-bis(dimethylamino)naphthalene (Br2DMAN), and its protonated (HBr) or deuterated (DBr) forms were studied by using x-ray diffraction and infrared spectroscopy, as well as ab initio and density functional theory calculations. In the crystalline lattice of the Br2DMAN.HBr salt, symmetrical (NHN)+ hydrogen bonding of length 2.547(3) Å is observed. No deuterium geometrical isotope effect was detected. The structure refinement suggests disordering of protons between two equivalent positions at the nitrogen atoms. These findings are in agreement with infrared spectra, which are characterized by an intense band centered at ∼560 cm−1 assigned to the ν(NHN) protonic transition. Deuteration leads to a shift of this band to ∼340 cm−1, so that the isotopic ratio νH/νD (ISR) of 1.65 is characteristic of an unusual potential for the proton motion. The results of MP2 calculations are in fairly good agreement with the experimental data. The theoretical N…N hydrogen bond length is 2.575 Å, while the distance between the minima equals to ca. 0.5 Å with a barrier height of 0.70 kcal/mol. The calculated difference between the 0→1 proton (deuteron) levels is 509 (284) cm−1, giving an ISR value of 1.76.</abstract><doi>10.1063/1.1594171</doi><tpages>7</tpages></addata></record> |
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title | Low barrier hydrogen bond in protonated proton sponge. X-ray diffraction, infrared, and theoretical ab initio and density functional theory studies |
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