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  • 1
    Publication Date: 2012-08-24
    Description: Materials exhibiting a spontaneous electrical polarization that can be switched easily between antiparallel orientations are of potential value for sensors, photonics and energy-efficient memories. In this context, organic ferroelectrics are of particular interest because they promise to be lightweight, inexpensive and easily processed into devices. A recently identified family of organic ferroelectric structures is based on intermolecular charge transfer, where donor and acceptor molecules co-crystallize in an alternating fashion known as a mixed stack: in the crystalline lattice, a collective transfer of electrons from donor to acceptor molecules results in the formation of dipoles that can be realigned by an external field as molecules switch partners in the mixed stack. Although mixed stacks have been investigated extensively, only three systems are known to show ferroelectric switching, all below 71 kelvin. Here we describe supramolecular charge-transfer networks that undergo ferroelectric polarization switching with a ferroelectric Curie temperature above room temperature. These polar and switchable systems utilize a structural synergy between a hydrogen-bonded network and charge-transfer complexation of donor and acceptor molecules in a mixed stack. This supramolecular motif could help guide the development of other functional organic systems that can switch polarization under the influence of electric fields at ambient temperatures.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Tayi, Alok S -- Shveyd, Alexander K -- Sue, Andrew C-H -- Szarko, Jodi M -- Rolczynski, Brian S -- Cao, Dennis -- Kennedy, T Jackson -- Sarjeant, Amy A -- Stern, Charlotte L -- Paxton, Walter F -- Wu, Wei -- Dey, Sanjeev K -- Fahrenbach, Albert C -- Guest, Jeffrey R -- Mohseni, Hooman -- Chen, Lin X -- Wang, Kang L -- Stoddart, J Fraser -- Stupp, Samuel I -- England -- Nature. 2012 Aug 23;488(7412):485-9. doi: 10.1038/nature11395.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/22914165" target="_blank"〉PubMed〈/a〉
    Keywords: Anisotropy ; Crystallization ; *Electricity ; Electron Transport ; *Electrons ; Hydrogen Bonding ; Iron/*chemistry ; Models, Molecular ; Molecular Conformation ; Organometallic Compounds/*chemistry ; Surface Properties ; *Temperature
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 2
    Publication Date: 2015-05-06
    Description: Multiple organic functionalities can now be apportioned into nanoscale domains within a metal-coordinated framework, posing the following question: how do we control the resulting combination of “heterogeneity and order”? Here, we report the creation of a metal–organic framework, MOF-2000, whose two component types are incorporated in a 2:1 ratio, even...
    Print ISSN: 0027-8424
    Electronic ISSN: 1091-6490
    Topics: Biology , Medicine , Natural Sciences in General
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  • 3
    Publication Date: 2016-11-27
    Description: Single-molecule electronic devices offer unique opportunities to investigate the properties of individual molecules that are not accessible in conventional ensemble experiments. However, these investigations remain challenging because they require (i) highly precise device fabrication to incorporate single molecules and (ii) sufficient time resolution to be able to make fast molecular dynamic measurements. We demonstrate a graphene-molecule single-molecule junction that is capable of probing the thermodynamic and kinetic parameters of a host-guest complex. By covalently integrating a conjugated molecular wire with a pendent crown ether into graphene point contacts, we can transduce the physical [2]pseudorotaxane (de)formation processes between the electron-rich crown ether and a dicationic guest into real-time electrical signals. The conductance of the single-molecule junction reveals two-level fluctuations that are highly dependent on temperature and solvent environments, affording a nondestructive means of quantitatively determining the binding and rate constants, as well as the activation energies, for host-guest complexes. The thermodynamic processes reveal the host-guest binding to be enthalpy-driven and are consistent with conventional 1 H nuclear magnetic resonance titration experiments. This electronic device opens up a new route to developing single-molecule dynamics investigations with microsecond resolution for a broad range of chemical and biochemical applications.
    Electronic ISSN: 2375-2548
    Topics: Natural Sciences in General
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