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      • The Chameleonic Nature of Diazaperopyrenium Recognition Processes

        Basuray, Ashish N.,Jacquot ,de ,Rouville, Henri‐,Pierre,Hartlieb, Karel J.,Kikuchi, Takashi,Strutt, Nathan L.,Bruns, Carson J.,Ambrogio, Michael W.,Avestro, Alyssa‐,Jennifer,Sc WILEY‐VCH Verlag 2012 Angewandte Chemie Vol.124 No.47

        <P><B>Zwei zum Preis von einem</B>: Das Diazaperopyrenium‐Dikation verhält sich sowohl homo‐ als auch heterophil, indem es mit seinesgleichen sowie mit vielfältigen π‐elektronenreichen Donoren Komplexe bildet. In Kombination mit den elektronischen Eigenschaften führt dieses dichotome Verhalten zur Bildung selbstorganisierter Nanodrähte im Festkörper sowie zu einer Templatwirkung bei der Bildung eines [3]‐ und zweier [2]Rotaxane mit aromatischen Kronenethern (siehe Bild).</P>

      • A Semiconducting Organic Radical Cationic Host–Guest Complex

        Fahrenbach, Albert C.,Sampath, Srinivasan,Late, Dattatray J.,Barnes, Jonathan C.,Kleinman, Samuel L.,Valley, Nicholas,Hartlieb, Karel J.,Liu, Zhichang,Dravid, Vinayak P.,Schatz, George C.,Van Duyne, R American Chemical Society 2012 ACS NANO Vol.6 No.11

        <P>The self-assembly and solid-state semiconducting properties of single crystals of a trisradical tricationic complex composed of the diradical dicationic cyclobis(paraquat-<I>p</I>-phenylene) (CBPQT<SUP>2(•+)</SUP>) ring and methyl viologen radical cation (MV<SUP>•+</SUP>) are reported. An organic field effect transistor incorporating single crystals of the CBPQT<SUP>2(•+)</SUP>⊂MV<SUP>•+</SUP> complex was constructed using lithographic techniques on a silicon substrate and shown to exhibit <I>p</I>-type semiconductivity with a mobility of 0.05 cm<SUP>2</SUP> V<SUP>–1</SUP> s<SUP>–1</SUP>. The morphology of the crystals on the silicon substrate was characterized using scanning electron microscopy which revealed that the complexes self-assemble into “molecular wires” observable by the naked-eye as millimeter long crystalline needles. The nature of the recognition processes driving this self-assembly, radical–radical interactions between bipyridinium radical cations (BIPY<SUP>•+</SUP>), was further investigated by resonance Raman spectroscopy in conjunction with theoretical investigations of the vibrational modes, and was supported by X-ray structural analyses of the complex and its free components in both their radical cationic and dicationic redox states. These spectroscopic investigations demonstrate that the bond order of the BIPY<SUP>•+</SUP> radical cationic units of host and guest components is not changed upon complexation, an observation which relates to its conductivity in the solid-state. We envision the modularity inherent in this kind of host–guest complexation could be harnessed to construct a library of custom-made electronic organic materials tailored to fit the specific needs of a given electronic application.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/ancac3/2012/ancac3.2012.6.issue-11/nn303553z/production/images/medium/nn-2012-03553z_0008.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/nn303553z'>ACS Electronic Supporting Info</A></P>

      • SCISCIESCOPUS

        A Radically Configurable Six-State Compound

        Barnes, J. C.,Fahrenbach, A. C.,Cao, D.,Dyar, S. M.,Frasconi, M.,Giesener, M. A.,Benitez, D.,Tkatchouk, E.,Chernyashevskyy, O.,Shin, W. H.,Li, H.,Sampath, S.,Stern, C. L.,Sarjeant, A. A.,Hartlieb, K. American Association for the Advancement of Scienc 2013 Science Vol.339 No.6118

        <P>Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis(paraquat-p-phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.</P>

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