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dc.contributor.authorBracco, Silvia
dc.contributor.authorBeretta, Mario
dc.contributor.authorCattaneo, Alice Silvia
dc.contributor.authorComotti, Angiolina
dc.contributor.authorFalqui, Andrea
dc.contributor.authorZhao, Ke
dc.contributor.authorRogers, Charles T.
dc.contributor.authorSozzani, Piero
dc.date.accessioned2015-08-03T12:30:18Z
dc.date.available2015-08-03T12:30:18Z
dc.date.issued2015-02-16
dc.identifier.issn14337851
dc.identifier.doi10.1002/anie.201412412
dc.identifier.urihttp://hdl.handle.net/10754/564060
dc.description.abstractNew mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p-divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 108 Hz at 325 K), as detected by solid-state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I2 vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl-fluoro-phenylene rotors, affecting their motion and the dielectric properties. Oriented molecular rotors: Fluorinated molecular rotors (see picture) were engineered in mesoporous hybrid organosilica architectures with crystalline order in their walls. The rotor dynamics was established by magic angle spinning NMR and dielectric measurements, indicating a rotational correlation time as short as 10-9 s at 325 K. The dynamics was modulated by I2 vapors entering the pores.
dc.description.sponsorshipA.C. would like to thank PRIN 2011 and Cariplo Foundation 2012. K.Z. and C.R. gratefully acknowledge financial support from the US National Science Foundation Division of Materials Research, through grant number DMR-1409981.
dc.publisherWiley-Blackwell
dc.subjectDielectric spectroscopy
dc.subjectHybrid materials
dc.subjectMolecular rotors
dc.subjectNMR spectroscopy
dc.subjectPorous materials
dc.titleDipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures
dc.typeArticle
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Division
dc.contributor.departmentBioscience Program
dc.identifier.journalAngewandte Chemie International Edition
dc.contributor.institutionDepartment of Materials Science, University of Milano Bicocca, Via R. Cozzi 55Milano, Italy
dc.contributor.institutionDepartment of Physics, University of Colorado Boulder, 2000 Colorado Ave.Boulder, CO, United States
kaust.personFalqui, Andrea


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