Small molecule-guided thermoresponsive supramolecular assemblies

Handle URI:
http://hdl.handle.net/10754/562372
Title:
Small molecule-guided thermoresponsive supramolecular assemblies
Authors:
Rancatore, Benjamin J.; Mauldin, Clayton E.; Frechet, Jean ( 0000-0001-6419-0163 ) ; Xu, Ting
Abstract:
Small organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.
KAUST Department:
Chemical Science Program; Physical Sciences and Engineering (PSE) Division
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
23-Oct-2012
DOI:
10.1021/ma301727q
Type:
Article
ISSN:
00249297
Sponsors:
This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the U.S. Department of Energy under Contract DE-AC02-05CH11231. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract DE-AC02-05CH11231.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program

Full metadata record

DC FieldValue Language
dc.contributor.authorRancatore, Benjamin J.en
dc.contributor.authorMauldin, Clayton E.en
dc.contributor.authorFrechet, Jeanen
dc.contributor.authorXu, Tingen
dc.date.accessioned2015-08-03T10:02:52Zen
dc.date.available2015-08-03T10:02:52Zen
dc.date.issued2012-10-23en
dc.identifier.issn00249297en
dc.identifier.doi10.1021/ma301727qen
dc.identifier.urihttp://hdl.handle.net/10754/562372en
dc.description.abstractSmall organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.en
dc.description.sponsorshipThis work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the U.S. Department of Energy under Contract DE-AC02-05CH11231. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract DE-AC02-05CH11231.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleSmall molecule-guided thermoresponsive supramolecular assembliesen
dc.typeArticleen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionDepartment of Chemistry, University of California, Berkeley, CA 94720-1460, United Statesen
dc.contributor.institutionDepartment of Material Sciences and Engineering, University of California, Berkeley, CA 94720-1460, United Statesen
dc.contributor.institutionDepartment of Chemical Engineering, University of California, Berkeley 94720-1460, United Statesen
dc.contributor.institutionMaterial Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, United Statesen
kaust.authorFrechet, Jeanen
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