Full Paper

Helicate Extension as a Route to Molecular Wires

  1. David Schultz1,
  2. Frédéric Biaso Dr.2,
  3. Abdul Rehaman Moughal Shahi2,
  4. Michel Geoffroy Prof. Dr.2,
  5. Kari Rissanen Prof. Dr.3,
  6. Laura Gagliardi Prof. Dr.2,
  7. Christopher J. Cramer Prof. Dr.4,
  8. Jonathan R. Nitschke Dr.5

Article first published online: 9 JUL 2008

DOI: 10.1002/chem.200800503

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 14, Issue 24, pages 7180–7185, August 18, 2008

Additional Information

How to Cite

Schultz, D., Biaso, F., Shahi, A., Geoffroy, M., Rissanen, K., Gagliardi, L., Cramer, C. and Nitschke, J. (2008), Helicate Extension as a Route to Molecular Wires. Chemistry - A European Journal, 14: 7180–7185. doi: 10.1002/chem.200800503

Author Information

  1. 1

    Department of Organic Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, 1211 Geneva (Switzerland)

  2. 2

    Department of Physical Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, 1211 Geneva (Switzerland), Fax: (+41) 22-37-96518

  3. 3

    Nanoscience Center, Department of Chemistry, University of Jyväskylä, P.O. Box 35, 40014 JYU (Finland), Fax: (+358) 14-260-2651

  4. 4

    Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455–0431 (USA), Fax: (+1) 612-626-2006

  5. 5

    University of Cambridge, Department of Chemistry, Lensfield Road, Cambridge CB2 1EW (UK), Fax: (+44) 1223-336017

Publication History

  1. Issue published online: 6 AUG 2008
  2. Article first published online: 9 JUL 2008
  3. Manuscript Received: 18 MAR 2008

Funded by

  • Walters-Kundert Charitable Trust
  • Swiss State Secretariat for Education and Research
  • Swiss National Science Foundation. Grant Numbers: 20EC21–112706, PP002–114828, 200020–120007
  • US National Science Foundation. Grant Number: CHE-0610183
  • Academy of Finland. Grant Number: 122350

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Keywords:

  • conducting materials;
  • coordination chemistry;
  • dynamic covalent chemistry;
  • self-assembly

Graphical Abstract

Thumbnail image of graphical abstract

Wiring itself: We demonstrate the use of self-assembly to prepare a well-defined piece of “molecular wire” containing four closely spaced, aligned copper(I) ions. Electrochemical studies and calculations indicate a high degree of electronic delocalization between the copper ions, which suggests that longer congeners constructed from more soluble building blocks might be useful molecular conductors (see figure).

Abstract

We describe the preparation of a helicate containing four closely spaced, linearly arrayed copper(I) ions. This product may be prepared either directly by mixing copper(I) with a set of precursor amine and aldehyde subcomponents, or indirectly through the dimerization of a dicopper(I) helicate upon addition of 1,2-phenylenediamine. A notable feature of this helicate is that its length is not limited by the lengths of its precursor subcomponents: each of the two ligands wrapped around the four copper(I) centers contains one diamine, two dialdehyde, and two monoamine residues. This work thus paves the way for the preparation of longer oligo- and polymeric structures. DFT calculations and electrochemical measurements indicate a high degree of electronic delocalization among the metal ions forming the cores of the structures described herein, which may therefore be described as “molecular wires”.

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