Massignani, Sara (2014) Auto-assemblaggio di Nuovi Polimeri di Coordinazione Basati sull’Unita' Trinucleare [Cu3(µ3-OH)(µ-pz)3]2+ (pz= ione pirazolato) e Mono- o Bicarbossilati. [Magistrali biennali]
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The self-assembling of CuII ions, pyrazole (Hpz), and mono- or bicarboxylate anions lead to different Coordination Polymers (CPs), mainly based on the triangular trinuclear cluster [Cu3(3-OH)(-Pz)3]2+. Using uncommon monocarboxylate ions, such as benzoate (Bnz), phenylacetate (Phac), phenylpropionate (Phpr), phenylacrylate (Phar) and vinylacetate (Vnac), new trinuclear and one mononuclear compounds were obtained. They were characterized by elemental analysis, IR spectroscopy and room temperature magnetic susceptibility measurement. The structures of the trinuclear CPs made with Phac and Phpr and of the mononuclear product with Bnz ion were identified by SC-XRD, whereas only cell parameters were found for the other compounds. In particular [Cu3(µ3-OH)(µ-pz)3(Phpr)2(Hpz)(H2O)]∙(H2O)x(MeOH)y shows a dodecanuclear cluster isolated for the first time in this work. The trinuclear compound obtained with Bnz anion has an interesting behavior in presence or in absence of solvent and it suggested the porosity of the framework. Using the terephthalate ion (Bdc), many trinuclear compounds were isolated employing different synthetic approaches. From the direct reaction of the terephthalate copper and Hpz even two mononuclear species were obtained, but they were already reported in licterature. Some new species were isolated from substitution reaction using [Cu3(µ3-OH)(µ-pz)3(CH3COO)2(Hpz)] e [Cu3(µ3-OH)(µ-pz)3(HCOO)2(Hpz)2(H2O)] and H2Bdc or Na2Bdc as reactants. In particular the diffusion method applied for the reaction of [Cu3(µ3-OH)(µ-pz)3(CH3COO)2(Hpz)] and Na2Bdc produced [Cu3(µ3-OH)(µ-pz)3(Bdc)(DMF)2] characterized by SC-XRD. The structure shows the formation of squared macrocycles which create a 2D network. Unfortunately adiacent networks are offset and so no pores and cavities are present.
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