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Pt-Tetraethynylethene Molecular Scaffolding: Synthesis and Characterization of a Novel Class of Organometallic Molecular Rods

2001; Wiley; Volume: 7; Issue: 6 Linguagem: Inglês

10.1002/1521-3765(20010316)7

1521-3765

Peter Siemsen, Ulrich Gubler, Christian Bosshard, Peter Günter, François Diederich,

Synthesis and Properties of Aromatic Compounds

Chemistry – A European JournalVolume 7, Issue 6 p. 1333-1341 Full Paper Pt-Tetraethynylethene Molecular Scaffolding: Synthesis and Characterization of a Novel Class of Organometallic Molecular Rods Peter Siemsen Dr., Peter Siemsen Dr. Laboratorium für Organische Chemie, ETH-Zentrum Universitätstrasse 16, 8092 Zürich (Switzerland) Fax: (+41) 1-632-1109Search for more papers by this authorUlrich Gubler Dr., Ulrich Gubler Dr. Nonlinear Optics Laboratory Institute of Quantum Electronics, ETH-Hönggerberg 8093 Zürich (Switzerland)Search for more papers by this authorChristian Bosshard Dr., Christian Bosshard Dr. Nonlinear Optics Laboratory Institute of Quantum Electronics, ETH-Hönggerberg 8093 Zürich (Switzerland)Search for more papers by this authorPeter Günter Prof. Dr., Peter Günter Prof. Dr. Nonlinear Optics Laboratory Institute of Quantum Electronics, ETH-Hönggerberg 8093 Zürich (Switzerland)Search for more papers by this authorFrançois Diederich Prof. Dr., François Diederich Prof. Dr. diederich@org.chem.ethz.ch Laboratorium für Organische Chemie, ETH-Zentrum Universitätstrasse 16, 8092 Zürich (Switzerland) Fax: (+41) 1-632-1109Search for more papers by this author Peter Siemsen Dr., Peter Siemsen Dr. Laboratorium für Organische Chemie, ETH-Zentrum Universitätstrasse 16, 8092 Zürich (Switzerland) Fax: (+41) 1-632-1109Search for more papers by this authorUlrich Gubler Dr., Ulrich Gubler Dr. Nonlinear Optics Laboratory Institute of Quantum Electronics, ETH-Hönggerberg 8093 Zürich (Switzerland)Search for more papers by this authorChristian Bosshard Dr., Christian Bosshard Dr. Nonlinear Optics Laboratory Institute of Quantum Electronics, ETH-Hönggerberg 8093 Zürich (Switzerland)Search for more papers by this authorPeter Günter Prof. Dr., Peter Günter Prof. Dr. Nonlinear Optics Laboratory Institute of Quantum Electronics, ETH-Hönggerberg 8093 Zürich (Switzerland)Search for more papers by this authorFrançois Diederich Prof. Dr., François Diederich Prof. Dr. diederich@org.chem.ethz.ch Laboratorium für Organische Chemie, ETH-Zentrum Universitätstrasse 16, 8092 Zürich (Switzerland) Fax: (+41) 1-632-1109Search for more papers by this author First published: 08 March 2001 https://doi.org/10.1002/1521-3765(20010316)7:6 3.0.CO;2-9Citations: 51Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract The synthesis of a new series of monodisperse organometallic molecular rods, extending in length from 3.3 to 12.1 nm (see diagram) provides another impressive example of the power of oxidative acetylenic homocouplings in the preparation of new nanomaterials. Measurements of optical and nonlinear optical properties showed that the Pt atoms act as insulating centers, thereby preventing π-electron delocalization along the linear oligomeric backbone. Abstract The series of monodisperse Pt-bridged TEE oligomers 3 a–f was prepared by oxidative Glaser–Hay oligomerization of monomer 7 under end-capping conditions. These novel molecular rods extend in length from 3.3 nm (monomeric 3 a) to 12.1 nm (hexameric 3 f). Their isolation was achieved by high performance gel permeation chromatography (GPC), and their purification was best monitored by analytical GPC in combination with matrix-assisted laser-desorption-ionization mass spectrometry (MALDI-TOF MS). The mass spectra of each oligomer revealed the molecular ion or its sodium complex as parent ion together with a clean, highly characteristic fragmentation pattern. Delayed addition of the end-capping reagent PhC≡CH to the oligomerization mixture afforded polymer 10 with an average of ≈32 repeat units and a remarkably narrow molecular weight distribution (Mw/Mn=1.06), which is indicative of a living polymerization process. UV/Vis spectral data as well as measurements of the second hyperpolarizability γ by third harmonic generation (THG) revealed a nearly complete lack of π-electron delocalization along the oligomeric backbone. The Pt atoms act as true insulating centers, and the Pt−C(sp) bonds hardly possess any π character. The synthesis of the molecular rods 3 a–f provides another demonstration of the power of oxidative acetylenic homocouplings for the preparation of unusual nanoarchitecture. Citing Literature Volume7, Issue6March 16, 2001Pages 1333-1341 RelatedInformation