{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,21]],"date-time":"2026-01-21T19:36:17Z","timestamp":1769024177991,"version":"3.49.0"},"reference-count":46,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2009,11,24]],"date-time":"2009-11-24T00:00:00Z","timestamp":1259020800000},"content-version":"vor","delay-in-days":23,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Helvetica Chimica Acta"],"published-print":{"date-parts":[[2009,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The three\u2010dimensional structures in aqueous solution of the entire series of the Ln<jats:sup>3+<\/jats:sup> complexes [Ln(DOTP*\u2010Et)]<jats:sup>\u2212<\/jats:sup> (formed from the free ligand <jats:italic>P<\/jats:italic>,<jats:italic>P\u2032<\/jats:italic>,<jats:italic>P\u2033<\/jats:italic>,<jats:italic>P\u2032\u2032\u2032<\/jats:italic>\u2010[1,4,7,10\u2010tetraazacyclododecane\u20101,4,7,10\u2010tetrayltetrakis(methylene)]tetrakis[<jats:italic>P<\/jats:italic>\u2010ethylphosphinic acid] (H<jats:sub>4<\/jats:sub>DOTP*\u2010Et) were studied by NMR techniques to rationalize the parameters governing the relaxivity of the Gd<jats:sup>3+<\/jats:sup> complex and evaluate its potential as MRI contrast agent. From the <jats:sup>1<\/jats:sup>H\u2010 and <jats:sup>31<\/jats:sup>P\u2010NMR lanthanide\u2010induced\u2010shift (LIS) values, especially of the [Yb(DOTP*\u2010Et)]<jats:sup>\u2212<\/jats:sup> complex, it was concluded that the [Ln(DOTP*\u2010Et)]<jats:sup>\u2212<\/jats:sup> complexes adopt in solution twisted square antiprismatic coordination geometries which change gradually their coordination\u2010cage structure along the lanthanide series. These complexes have no inner\u2010sphere\u2010H<jats:sub>2<\/jats:sub>O coordination, and preferentially have the (<jats:italic>R<\/jats:italic>,<jats:italic>R<\/jats:italic>,<jats:italic>R<\/jats:italic>,<jats:italic>R<\/jats:italic>) configuration of the P\u2010atoms in the pendant arms. Self\u2010association was observed in aqueous solution for the tetraazatetrakisphosphonic acid ester complexes [Ln(DOTP*\u2010OEt)]<jats:sup>\u2212<\/jats:sup> (=[Ln(DOTP\u2010Et)]<jats:sup>\u2212<\/jats:sup>) and [Ln(DOTP*\u2010OBu)]<jats:sup>\u2212<\/jats:sup> (=[Ln(DOTP\u2010Bu)]<jats:sup>\u2212<\/jats:sup>) at and above 5\u2005m<jats:sc>M<\/jats:sc> concentration, through analysis of <jats:sup>31<\/jats:sup>P\u2010NMR, EPR, vapor\u2010pressure\u2010osmometry, and luminescence\u2010spectroscopic data. The presence of the cationic detergent cetylpyridinium chloride (CPC; but not of neutral surfactants) shifts the isomer equilibrium of [Eu(DOTP*\u2010OBu)]<jats:sup>\u2212<\/jats:sup> to the (<jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>) form which selectively binds to the cationic micelle surface.<\/jats:p>","DOI":"10.1002\/hlca.200900160","type":"journal-article","created":{"date-parts":[[2009,11,24]],"date-time":"2009-11-24T06:28:24Z","timestamp":1259044104000},"page":"2532-2551","source":"Crossref","is-referenced-by-count":19,"title":["NMR Characterization of Lanthanide(3+) Complexes of Tetraazatetrakisphosphinato and Tetraazatetra\u00adkisphosphonato 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