The reactivity of CO2 with polyamino substrates based on calix[4]arenes and on a difunctional, noncyclic model has been studied. All the compounds react with CO2 in chloroform to form ammonium carb innate salts. However, the number, topology, and conformational features of the amino-functionalized arms present on the multivalent scaffold have a remarkable influence on the reaction efficiency and on the product composition. Tetraaminocalix[4]arenes 1-3 rapidly and efficiently react with 2 equiv of CO2, yielding highly stable hydrogen-bonded dimers formed by the self-assembly of two bis-ammonium bis-carbamate intramolecular salts. 1,3-Diaminocalix[4]arene 4 absorbs 1 mol of CO2, affording less stable zwitterionic ammonium carbamates. Gemini compound 5 reacts with CO2 in a 1:1 stoichiometry, forming hydrogen. bonded dimers of ammonium carbamate derivatives of moderate stability. For upper rim 1,3-diaminocalix[4]arene 6, in addition to the labile intramolecular salt, the presence of a self-assembled polymer was also detected. These systems were fully characterized in solution by H-1 and C-13 NMR spectroscopy, whereas the corresponding gas-solid reactions were further investigated by QCM measurements. Interestingly, the high affinity and reversibility of CO2 uptake shown by 1,3-diamino calix[4]arene 4 enabled us to attain a promising QCM device for carbon dioxide sensing.

CO2 Capture by Multivalent Amino-functionalized Calixarenes: Self-Assembly, Absorption and QCM Detection Studies / Baldini, Laura; Melegari, Monica; Bagnacani, Valentina; Casnati, Alessandro; Dalcanale, Enrico; Sansone, Francesco; Ungaro, Rocco. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 76:(2011), pp. 3720-3732. [10.1021/jo200650f]

CO2 Capture by Multivalent Amino-functionalized Calixarenes: Self-Assembly, Absorption and QCM Detection Studies

BALDINI, Laura;MELEGARI, Monica;BAGNACANI, Valentina;CASNATI, Alessandro;DALCANALE, Enrico;SANSONE, Francesco;UNGARO, Rocco
2011-01-01

Abstract

The reactivity of CO2 with polyamino substrates based on calix[4]arenes and on a difunctional, noncyclic model has been studied. All the compounds react with CO2 in chloroform to form ammonium carb innate salts. However, the number, topology, and conformational features of the amino-functionalized arms present on the multivalent scaffold have a remarkable influence on the reaction efficiency and on the product composition. Tetraaminocalix[4]arenes 1-3 rapidly and efficiently react with 2 equiv of CO2, yielding highly stable hydrogen-bonded dimers formed by the self-assembly of two bis-ammonium bis-carbamate intramolecular salts. 1,3-Diaminocalix[4]arene 4 absorbs 1 mol of CO2, affording less stable zwitterionic ammonium carbamates. Gemini compound 5 reacts with CO2 in a 1:1 stoichiometry, forming hydrogen. bonded dimers of ammonium carbamate derivatives of moderate stability. For upper rim 1,3-diaminocalix[4]arene 6, in addition to the labile intramolecular salt, the presence of a self-assembled polymer was also detected. These systems were fully characterized in solution by H-1 and C-13 NMR spectroscopy, whereas the corresponding gas-solid reactions were further investigated by QCM measurements. Interestingly, the high affinity and reversibility of CO2 uptake shown by 1,3-diamino calix[4]arene 4 enabled us to attain a promising QCM device for carbon dioxide sensing.
2011
CO2 Capture by Multivalent Amino-functionalized Calixarenes: Self-Assembly, Absorption and QCM Detection Studies / Baldini, Laura; Melegari, Monica; Bagnacani, Valentina; Casnati, Alessandro; Dalcanale, Enrico; Sansone, Francesco; Ungaro, Rocco. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 76:(2011), pp. 3720-3732. [10.1021/jo200650f]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2351178
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