On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids
The HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs) via the measurement of the cross relaxation rate σ between two spins. In the intermolecular case, σ is proportional to r − n , where r is the internuc...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2018, Vol.2 (19), p.13357-13364 |
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| creator | Martin, Pierre-Alexandre Salager, Elodie Forsyth, Maria O'Dell, Luke A Deschamps, Michaël |
| description | The HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs)
via
the measurement of the cross relaxation rate
σ
between two spins. In the intermolecular case,
σ
is proportional to
r
−
n
, where
r
is the internuclear distance and
n
can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus
σ
can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for
σ
are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for
7
Li-
1
H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.
Intermolecular cross relaxation rates are measured in an ionic liquid electrolyte and interpreted in terms of closest distances between cations. |
| doi_str_mv | 10.1039/c8cp00911b |
| format | Article |
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via
the measurement of the cross relaxation rate
σ
between two spins. In the intermolecular case,
σ
is proportional to
r
−
n
, where
r
is the internuclear distance and
n
can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus
σ
can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for
σ
are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for
7
Li-
1
H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.
Intermolecular cross relaxation rates are measured in an ionic liquid electrolyte and interpreted in terms of closest distances between cations.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/c8cp00911b</identifier><identifier>PMID: 29718051</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Chemical Sciences ; Cross relaxation ; Ionic liquids ; Ions ; Lithium isotopes ; Material chemistry ; NMR ; Nuclear magnetic resonance ; Overhauser effect ; Solid phases ; Solvents</subject><ispartof>Physical chemistry chemical physics : PCCP, 2018, Vol.2 (19), p.13357-13364</ispartof><rights>Copyright Royal Society of Chemistry 2018</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c449t-b23a68efc38d1e2c0330cde1614350d6b3c3576e3de1968438440235b80642883</citedby><cites>FETCH-LOGICAL-c449t-b23a68efc38d1e2c0330cde1614350d6b3c3576e3de1968438440235b80642883</cites><orcidid>0000-0002-5443-9698 ; 0000-0002-7760-5417 ; 0000-0002-4273-8105 ; 0000-0001-8309-3932</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,4010,27900,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29718051$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-01898343$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Martin, Pierre-Alexandre</creatorcontrib><creatorcontrib>Salager, Elodie</creatorcontrib><creatorcontrib>Forsyth, Maria</creatorcontrib><creatorcontrib>O'Dell, Luke A</creatorcontrib><creatorcontrib>Deschamps, Michaël</creatorcontrib><title>On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>The HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs)
via
the measurement of the cross relaxation rate
σ
between two spins. In the intermolecular case,
σ
is proportional to
r
−
n
, where
r
is the internuclear distance and
n
can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus
σ
can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for
σ
are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for
7
Li-
1
H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.
Intermolecular cross relaxation rates are measured in an ionic liquid electrolyte and interpreted in terms of closest distances between cations.</description><subject>Chemical Sciences</subject><subject>Cross relaxation</subject><subject>Ionic liquids</subject><subject>Ions</subject><subject>Lithium isotopes</subject><subject>Material chemistry</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Overhauser effect</subject><subject>Solid phases</subject><subject>Solvents</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpdkU1PwzAMhiMEgvFx4Q6KxAWQBkmdtslxTHxJk8YBLlyqNPW0TmkzkhbBvydjMCROzms_duK8hBxzdsUZqGsjzZIxxXm5RQZcZDBUTIrtzTnP9sh-CAvGGE857JK9ROVcspQPyOu0pd0caYM69B4bbDvqZrRuO_SNs2h6qz2dY5Su7Y3FqIx3IVCPVn_ornYt9brDEHtoFLWhtn7r6yockp2ZtgGPfuIBebm7fR4_DCfT-8fxaDI0QqhuWCagM4kzA7LimBgGwEyFPOMCUlZlJRhI8wwh5lQmBUghWAJpKVkmEinhgFys5861LZa-brT_LJyui4fRpFjlGJdKgoB3HtnzNbv07q3H0BVNHQxaq1t0fSiSeDvIPJdpRM_-oQvX-zZusqKUFEokKlKXa-r7UzzONi_grFi5U4zl-OnbnZsIn_6M7MsGqw36a0cETtaAD2ZT_bMXvgD0OpIi</recordid><startdate>2018</startdate><enddate>2018</enddate><creator>Martin, Pierre-Alexandre</creator><creator>Salager, Elodie</creator><creator>Forsyth, Maria</creator><creator>O'Dell, Luke A</creator><creator>Deschamps, Michaël</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0002-5443-9698</orcidid><orcidid>https://orcid.org/0000-0002-7760-5417</orcidid><orcidid>https://orcid.org/0000-0002-4273-8105</orcidid><orcidid>https://orcid.org/0000-0001-8309-3932</orcidid></search><sort><creationdate>2018</creationdate><title>On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids</title><author>Martin, Pierre-Alexandre ; Salager, Elodie ; Forsyth, Maria ; O'Dell, Luke A ; Deschamps, Michaël</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c449t-b23a68efc38d1e2c0330cde1614350d6b3c3576e3de1968438440235b80642883</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Chemical Sciences</topic><topic>Cross relaxation</topic><topic>Ionic liquids</topic><topic>Ions</topic><topic>Lithium isotopes</topic><topic>Material chemistry</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Overhauser effect</topic><topic>Solid phases</topic><topic>Solvents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Martin, Pierre-Alexandre</creatorcontrib><creatorcontrib>Salager, Elodie</creatorcontrib><creatorcontrib>Forsyth, Maria</creatorcontrib><creatorcontrib>O'Dell, Luke A</creatorcontrib><creatorcontrib>Deschamps, Michaël</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Martin, Pierre-Alexandre</au><au>Salager, Elodie</au><au>Forsyth, Maria</au><au>O'Dell, Luke A</au><au>Deschamps, Michaël</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2018</date><risdate>2018</risdate><volume>2</volume><issue>19</issue><spage>13357</spage><epage>13364</epage><pages>13357-13364</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs)
via
the measurement of the cross relaxation rate
σ
between two spins. In the intermolecular case,
σ
is proportional to
r
−
n
, where
r
is the internuclear distance and
n
can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus
σ
can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for
σ
are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for
7
Li-
1
H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.
Intermolecular cross relaxation rates are measured in an ionic liquid electrolyte and interpreted in terms of closest distances between cations.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>29718051</pmid><doi>10.1039/c8cp00911b</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-5443-9698</orcidid><orcidid>https://orcid.org/0000-0002-7760-5417</orcidid><orcidid>https://orcid.org/0000-0002-4273-8105</orcidid><orcidid>https://orcid.org/0000-0001-8309-3932</orcidid></addata></record> |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Chemical Sciences Cross relaxation Ionic liquids Ions Lithium isotopes Material chemistry NMR Nuclear magnetic resonance Overhauser effect Solid phases Solvents |
| title | On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids |
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