{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T03:22:27Z","timestamp":1791170547281,"version":"4.1.0"},"reference-count":47,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2004,3,16]],"date-time":"2004-03-16T00:00:00Z","timestamp":1079395200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2004,4,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Pulsed field gradient <jats:sup>1<\/jats:sup>H NMR spectroscopy has been applied to investigate the association behavior of the Sn<jats:sub>12<\/jats:sub>\u2013oxo cluster macrocation [(BuSn)<jats:sub>12<\/jats:sub>O<jats:sub>14<\/jats:sub>(OH)<jats:sub>6<\/jats:sub>]<jats:sup>2+<\/jats:sup> with two different and smaller anions, <jats:italic>p<\/jats:italic>\u2010toluenesulfonate (PTS<jats:sup>\u2212<\/jats:sup>) and diphenylphosphinate (Ph<jats:sub>2<\/jats:sub>PO<jats:sub>2<\/jats:sub><jats:sup>\u2212<\/jats:sup>). By monitoring the translational diffusion coefficients of the various species involved, it is shown that the association depends on the anion involved and on the solvent used. Moreover, the possibility to individually monitor the diffusion characteristics of multiple anionic and cationic species in mixtures, by virtue of resolved <jats:sup>1<\/jats:sup>H resonances available from each species, allows us to evidence the occurrence of ion exchange in such systems. Thus when [(BuSn)<jats:sub>12<\/jats:sub>O<jats:sub>14<\/jats:sub>(OH)<jats:sub>6<\/jats:sub>](PTS)<jats:sub>2<\/jats:sub> is mixed with two equivalents of Ph<jats:sub>2<\/jats:sub>PO<jats:sub>2<\/jats:sub>NMe<jats:sub>4<\/jats:sub>, PTS<jats:sup>\u2212<\/jats:sup> is displaced by Ph<jats:sub>2<\/jats:sub>PO<jats:sub>2<\/jats:sub><jats:sup>\u2212<\/jats:sup>, highlighting the greater affinity of the organotin macrocation for the diphenylphosphinate. This example clearly illustrates the potential of pulsed field gradient <jats:sup>1<\/jats:sup>H NMR spectroscopy in inorganic\/organometallic chemistry, to follow preferential ion pairing in multi\u2010ion systems at the level of each individually charged species.<\/jats:p>","DOI":"10.1002\/chem.200305604","type":"journal-article","created":{"date-parts":[[2004,3,25]],"date-time":"2004-03-25T13:59:58Z","timestamp":1080223198000},"page":"1747-1751","source":"Crossref","is-referenced-by-count":29,"title":["Probing Ionic Association on Metal Oxide Clusters by Pulsed Field Gradient NMR Spectroscopy: The Example of Sn<sub>12<\/sub>\u2013Oxo Clusters"],"prefix":"10.1002","volume":"10","author":[{"given":"Fran\u00e7ois","family":"Ribot","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Virginie","family":"Escax","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jos\u00e9 C.","family":"Martins","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Monique","family":"Biesemans","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Laurent","family":"Ghys","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ingrid","family":"Verbruggen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rudolph","family":"Willem","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2004,3,24]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(89)85043-0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(94)84137-3"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00129a023"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic971189r"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990877a"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om000588i"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1515\/MGMC.2000.23.7.331"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm011061e"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-4095(20021016)14:20<1496::AID-ADMA1496>3.0.CO;2-N"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990973b"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1695690"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0079-6565(99)00003-5"},{"key":"e_1_2_6_15_2","unstructured":"\u00a0"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1006\/jmrb.1995.1118"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9817366"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0079-6565(02)00049-3"},{"key":"e_1_2_6_19_2","unstructured":"For a review see:"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/1522-2675(20011017)84:10<2833::AID-HLCA2833>3.0.CO;2-O"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9703115"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/om000574c"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/om030145p"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0209780"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0206600"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034549l"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1039\/a908203d"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0346375"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9931933"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002278x"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020104)114:1<114::AID-ANGE114>3.0.CO;2-D"},{"key":"e_1_2_6_31_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020104)41:1<107::AID-ANIE107>3.0.CO;2-N"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/b108325m"},{"key":"e_1_2_6_33_2","unstructured":"The size of [(BuSn)12O14(OH)6]2+was estimated by two independent methods. According to the molecular structures determined by single\u2010crystal X\u2010ray diffraction [1]a sphere of \u223c8.5 \u00c5 of radius contains the macrocation.119SnT1measurements can also provide information on the hydrodynamic radius of the organotin\u2013oxo clusters. Indeed for such species the main119Sn relaxation mechanism is chemical shift anisotropy (CSA).T1CSAcan be related to the chemical shift anisotropy (\u03b6) and asymmetry (\u03c6) as well as to the correlation time which depends on the viscosity of the medium and on the hydrodynamic diameter through the Debye\u2013Stokes\u2013Einstein relation (\u03c4c=4\u03c0\u03b7rH3\/3kBT).[18]According to theT1values of2in CD2Cl2(0.20 and 0.15 s for the six\u2010 and five\u2010coordinate tin atoms respectively)[1\u2009e]and to its119Sn chemical shift anisotropy parameters (\u03b6=320 ppm \u03c6=0.2 and\u03b6=390 ppm \u03c6=0.3 for the six\u2010 and five\u2010coordinate tin atoms respectively)[1\u2009e]as determined by119Sn MAS NMR spectroscopy a hydrodynamic radius of 9.5 \u00c5 which includes two bondedp\u2010toluenesulfonates can be computed for2."},{"key":"e_1_2_6_34_2","unstructured":"The size of Ph2PO2\u2212and PTS\u2212was estimated from their molecular structures as the radius of the sphere centered on their geometrical center (rG) or on their mass center (rM) and which includes all the atoms. The values arerG=4.75 rM=4.95 \u00c5 for Ph2PO2\u2212andrG=3.8 rM=4.8 \u00c5 for PTS\u2212. The large difference betweenrGandrMfor PTS\u2212is linked to the clear disymmetry brought by the sulfonate group. However for PTS\u2212 the elongated shape of the molecule makes the \u201cglobular\u201d approximation less reasonable."},{"key":"e_1_2_6_35_2","volume-title":"Theory of Simple Liquids","author":"Hansen J. P.","year":"1960"},{"key":"e_1_2_6_36_2","first-page":"6","volume-title":"Handbook of Chemistry and Physics","year":"2001"},{"key":"e_1_2_6_37_2","first-page":"6","volume-title":"Handbook of Chemistry and Physics","year":"2001"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/mrc.917"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(00)00492-0"},{"key":"e_1_2_6_40_2","unstructured":"\u00a0"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00187a028"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00161a044"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/0277-5387(95)85009-0"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1006\/jmra.1995.1176"},{"key":"e_1_2_6_45_2","unstructured":"DOSY and Diffusion by NMR Bruker Users Guide for XWinNMR 3.1 and 3.5 2002."},{"key":"e_1_2_6_46_2","first-page":"316","volume-title":"Les Principes du Magn\u00e9tisme Nucl\u00e9aire","author":"Abragam A.","year":"1961"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200305604","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200305604","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T16:09:53Z","timestamp":1760285393000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200305604"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2004,3,24]]},"references-count":47,"journal-issue":{"issue":"7","published-print":{"date-parts":[[2004,4,2]]}},"alternative-id":["10.1002\/chem.200305604"],"URL":"https:\/\/doi.org\/10.1002\/chem.200305604","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2004,3,24]]}}}