{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T14:40:01Z","timestamp":1760366401901,"version":"build-2065373602"},"reference-count":70,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2012,4,12]],"date-time":"2012-04-12T00:00:00Z","timestamp":1334188800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Inorg Chem"],"published-print":{"date-parts":[[2012,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The lanthanide (Ln<jats:sup>3+<\/jats:sup>) complexes of three cyclen\u2010based ligands containing three methylphosphonate pendant arms were studied, the ligands being 1,4,7,10\u2010tetraazacyclododecane\u20101,4,7\u2010triyltris(methylphosphonic acid) (H<jats:sub>6<\/jats:sub>do3p), 3\u2010[4,7,10\u2010tris(phosphonomethyl)\u20101,4,7,10\u2010tetraazacyclododec\u20101\u2010yl]propanoic acid (H<jats:sub>7<\/jats:sub>do3p1pr), and 10\u2010(3\u2010hydroxypropyl)\u20101,4,7,10\u2010tetraazacyclododecane\u20101,4,7\u2010triyltris(methylphosphonic acid) (H<jats:sub>6<\/jats:sub>do3p1ol). The three macrocyclic ligands form complexes of very high thermodynamic stability with all studied Ln<jats:sup>3+<\/jats:sup> ions. Kinetic studies showed that the acid\u2010assisted dissociation of Ce<jats:sup>3+<\/jats:sup> complexes of these ligands is much faster than for the complex of the related ligand H<jats:sub>8<\/jats:sub>dotp [1,4,7,10\u2010tetraazacyclododecane\u20101,4,7,10\u2010tetrayltetrakis(methylphosphonic acid)]. The number of water molecules coordinated to the Eu<jats:sup>3+<\/jats:sup> and Gd<jats:sup>3+<\/jats:sup> complexes was estimated to be &lt; 1 for the do3p1ol ligand but ca. 1 for the other two ligands, as obtained by time\u2010resolved luminescence spectroscopy and by <jats:sup>1<\/jats:sup>H and <jats:sup>17<\/jats:sup>O relaxometric measurements. The NMR spectroscopic data indicate the existence of a considerable contribution from second\u2010sphere water molecules to the relaxivity of all the Gd<jats:sup>3+<\/jats:sup> complexes studied. The <jats:sup>1<\/jats:sup>H and <jats:sup>31<\/jats:sup>P NMR spectra of the Eu<jats:sup>3+<\/jats:sup>, Yb<jats:sup>3+<\/jats:sup> and Lu<jats:sup>3+<\/jats:sup> complexes showed that the propionate arm in the [Ln(do3p1pr)]<jats:sup>4\u2013<\/jats:sup> complexes and the propanol arm in the [Ln(do3p1ol)]<jats:sup>3\u2013<\/jats:sup> complexes are not bound to the Ln<jats:sup>3+<\/jats:sup> ion. The [Ln(do3p)]<jats:sup>3\u2013<\/jats:sup> and [Ln(do3p1pr)]<jats:sup>4\u2013<\/jats:sup> complexes have a clear preference for the TSAP (twisted square antiprismatic) isomer, while both SAP (square antiprismatic) and TSAP isomers are present in solutions of the [Ln(do3p1ol)]<jats:sup>3\u2013<\/jats:sup> complexes.<\/jats:p>","DOI":"10.1002\/ejic.201101335","type":"journal-article","created":{"date-parts":[[2012,4,12]],"date-time":"2012-04-12T05:55:17Z","timestamp":1334210117000},"page":"2548-2559","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln<sup>3+<\/sup> Complexes"],"prefix":"10.1002","volume":"2012","author":[{"given":"Lu\u00eds M. 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