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Potentiometric studies performed at 298.2\u2005K in MeOH\/H<jats:sub>2<\/jats:sub>O (50:50 <jats:italic>v<\/jats:italic>\/<jats:italic>v<\/jats:italic>) and at ionic strength 0.10\u2005mol\u2009dm<jats:sup>\u22123<\/jats:sup> in KNO<jats:sub>3<\/jats:sub> revealed that trinuclear species predominate in solution from pH\u20055.0, the hydroxo complexes being the main species, which start forming at unusual very low pH values. The single\u2010crystal X\u2010ray determination of the trinuclear complex showed that the three copper centres have square\u2010planar geometry, arranged in an almost equilateral triangle, and have carbonate bridging the three metal centres. The presence of carbonate resulted from fixation of atmospheric CO<jats:sub>2<\/jats:sub>. The present study represents the first \u03bc<jats:sub>3<\/jats:sub>\u2010CO<jats:sub>3<\/jats:sub>\u2010bridged trinuclear copper(II) complex located in the interior of a macrobicyclic cavity. The magnetic data of [Cu<jats:sub>3<\/jats:sub>(pyr)(\u03bc<jats:sub>3<\/jats:sub>\u2010CO<jats:sub>3<\/jats:sub>)]<jats:bold>\u22c5<\/jats:bold>(ClO<jats:sub>4<\/jats:sub>)<jats:sub>4<\/jats:sub> showed ferromagnetic intramolecular interactions [<jats:italic>J<\/jats:italic>=3.80\u2005cm<jats:sup>\u22121<\/jats:sup>, based on the Hamiltonian <jats:italic>H<\/jats:italic>=\u2212<jats:italic>J<\/jats:italic>(<jats:italic>S<\/jats:italic><jats:sub>1<\/jats:sub><jats:italic>S<\/jats:italic><jats:sub>2<\/jats:sub>+<jats:italic>S<\/jats:italic><jats:sub>2<\/jats:sub><jats:italic>S<\/jats:italic><jats:sub>3<\/jats:sub>+<jats:italic>S<\/jats:italic><jats:sub>1<\/jats:sub><jats:italic>S<\/jats:italic><jats:sub>3<\/jats:sub>)] yielding a spin quartet, <jats:italic>S<\/jats:italic>=3\/2, ground state. Density functional calculations on the experimental geometry of the trinuclear complex showed that the ferromagnetic nature of the magnetic coupling can be attributed to the <jats:italic>syn<\/jats:italic>\u2013<jats:italic>anti<\/jats:italic> conformation of the carbonato bridge, and a magneto\u2010structural correlation, based on the different conformations (<jats:italic>syn<\/jats:italic>\u2013<jats:italic>anti<\/jats:italic>, <jats:italic>syn<\/jats:italic>\u2013<jats:italic>syn<\/jats:italic> and <jats:italic>anti<\/jats:italic>\u2013<jats:italic>anti<\/jats:italic>), is presented. The interesting properties observed, namely the lowering of the p<jats:italic>K<\/jats:italic><jats:sub>a<\/jats:sub> of coordinated water molecules to unusual values and the good fit of the carbonate anion between the copper centres, derive from the special architecture of pyr.<\/jats:p>","DOI":"10.1002\/chem.201101372","type":"journal-article","created":{"date-parts":[[2011,8,31]],"date-time":"2011-08-31T18:09:18Z","timestamp":1314814158000},"page":"11193-11203","source":"Crossref","is-referenced-by-count":47,"title":["A Trinuclear Copper(II) Cryptate and Its \u03bc<sub>3<\/sub>\u2010CO<sub>3<\/sub> Cascade Complex: Thermodynamics, Structural and Magnetic 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