Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures

Handle URI:
http://hdl.handle.net/10754/564060
Title:
Dipolar rotors orderly aligned in mesoporous fluorinated organosilica architectures
Authors:
Bracco, Silvia; Beretta, Mario; Cattaneo, Alice Silvia; Comotti, Angiolina; Falqui, Andrea ( 0000-0002-1476-7742 ) ; Zhao, Ke; Rogers, Charles T.; Sozzani, Piero
Abstract:
New 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.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; Bioscience Program
Publisher:
Wiley-Blackwell
Journal:
Angewandte Chemie International Edition
Issue Date:
16-Feb-2015
DOI:
10.1002/anie.201412412
Type:
Article
ISSN:
14337851
Sponsors:
A.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.
Appears in Collections:
Articles; Bioscience Program; Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorBracco, Silviaen
dc.contributor.authorBeretta, Marioen
dc.contributor.authorCattaneo, Alice Silviaen
dc.contributor.authorComotti, Angiolinaen
dc.contributor.authorFalqui, Andreaen
dc.contributor.authorZhao, Keen
dc.contributor.authorRogers, Charles T.en
dc.contributor.authorSozzani, Pieroen
dc.date.accessioned2015-08-03T12:30:18Zen
dc.date.available2015-08-03T12:30:18Zen
dc.date.issued2015-02-16en
dc.identifier.issn14337851en
dc.identifier.doi10.1002/anie.201412412en
dc.identifier.urihttp://hdl.handle.net/10754/564060en
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.en
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.en
dc.publisherWiley-Blackwellen
dc.subjectDielectric spectroscopyen
dc.subjectHybrid materialsen
dc.subjectMolecular rotorsen
dc.subjectNMR spectroscopyen
dc.subjectPorous materialsen
dc.titleDipolar rotors orderly aligned in mesoporous fluorinated organosilica architecturesen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentBioscience Programen
dc.identifier.journalAngewandte Chemie International Editionen
dc.contributor.institutionDepartment of Materials Science, University of Milano Bicocca, Via R. Cozzi 55Milano, Italyen
dc.contributor.institutionDepartment of Physics, University of Colorado Boulder, 2000 Colorado Ave.Boulder, CO, United Statesen
kaust.authorFalqui, Andreaen
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