Forlin, Enrico (2011) Nuovi Polimeri di Coordinazione Mediante Autoassemblaggio dell'Unità Trinucleare [Cu3(3-OH)(-Pz)3]2+ ed Anioni Bicarbossilato. [Laurea specialistica biennale]
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The self-assembling of CuII ions, pyrazole (HPz), and bicarboxylate anions lead to different Coordination Polymers (CPs), based on the triangular trinuclear cluster [Cu3(3-OH)(-Pz)]2+ or on mononuclear units. Using the bicarboxylate ions succinate (Succ), glutarate (Glut), adipate (Ad), methylfumarate (Mesac) and fumarate (Fum) and employing different synthetic approaches, new trinuclear and mononuclear compounds were obtained. They were characterized by elemental analysis, IR spectroscopy, XRPD and room temperature magnetic susceptibility measurement and their structures were identified by SC-XRD. Trinuclear compounds [Cu3(3-OH)(-Pz)3(Succ)] (Str2), [Cu3(3-OH)(-Pz)3(Succ)(H2O)2]∙(H2O)x(MeOH)y (Str3), [Cu3(3-OH)(-Pz)3(Glut)(DMF)0.5] (Gtr4) and -[Cu3(3-OH)(-Pz)3(Ad)] (Atr2) assemble forming 3D frameworks, while [Cu3(3-OH)(-Pz)3(Mesac)(HPz)] (Mstr1) and [Cu3(3-OH)(-Pz)3(Fum)(HPz)] (Ftr1) present a 2D network and [Cu3(3-OH)(-Pz)3(Glut)(HPz)(H2O)2]∙0.5H2O (Gtr5) has a polymeric one-dimensional extension. Mononuclear compounds [Cu(HSucc)2(HPz)4] (Sm2) and [Cu(HGlut)2(HPz)4] (Gm2) have a molecular structure, while [Cu(Mesac)(HPz)2(H2O)]∙H2O (Msm1) is a one-dimensional CP. The structures characterized present common trinuclear units self-assembling, particularly the coupling in hexanuclear units (Str2, Gtr5, Atr2, Mstr1 and Ftr1) and the formation of six-units rings (Str3, Gtr4 and Atr2). Moreover, Mstr1 and Ftr1 are isoreticular. Compounds Str3 and Gtr4 have 3D channels, which are occupied by solvent molecules (Str3) or empty (Gtr4). These compounds are air stable and interesting for future application as sorption of small molecules.
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