Project

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Functional organic and organometallic materials for molecular electronic applications

English title Functional organic and organometallic materials for molecular electronic applications
Applicant Berke Heinz
Number 126142
Funding scheme NRP 62 Smart Materials
Research institution Institut für Chemie Universität Zürich
Institution of higher education University of Zurich - ZH
Main discipline Inorganic Chemistry
Start/End 01.03.2010 - 31.03.2015
Approved amount 680'939.00
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All Disciplines (3)

Discipline
Inorganic Chemistry
Organic Chemistry
Physical Chemistry

Keywords (5)

Molecular electronics; Molecular wires; Electronic devices; Organometallic materials; Organic materials

Lay Summary (English)

Lead
Lay summary
Functional organic and organometallic materials for molecular electronic applications

A promising strategy towards technology at the nanometer scale is offered by a bottom-up approach, which starts from atoms or molecules and builds up nanostructures. The integration of transition metal atoms opens potential applications in molecular electronics, particularly due to the fact that metals can promote charge transport.

Background
Organometallic complexes with integrated transition metals having two different electronic states have the potential to be applied as memory elements. Upon removing an electron from the molecule, by applying high voltage, the molecule is oxidized and the conduction state is switched on (write process). Once the applied voltage is removed, the molecule retains its oxidized state (memory). Upon applying the reversed voltage, the molecule returns to its original oxidation state (erase process). Probing the conduction states of molecules by applying low voltage is a reading process. However, the abilities of organometallic complexes at the single
molecular level have not yet been thoroughly explored.

Aim
Correlation of the molecular structure and electronic properties will be studied. The project aims at a detailed understanding and exploitation of the internal molecular mechanisms and processes, which can be used for radically new approaches in future nanoscale electronic devices.

Significance
The knowledge gained within this project is a prerequisite for the future use of small ensembles or even individual molecules as functional building blocks in electronic
circuitry. Single-molecule devices are ideal candidates for future nano-electronics, as they possess the potential for creating high-density devices with low-power consumption in combination with high speed.

Application
The molecular materials in the current project are designed to allow the testing of these materials for electronic applications. The development of new smart materials that are able to switch by a voltage trigger between at least two states should lead to memory applications. Molecular devices taking advantage of self-assembly processes will also have low manufacturing costs. Moreover, because of their internal molecular structure, molecules may provide radically new and intrinsic functionalities not found in today’s conventional semiconductor-based electronics.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Structural and Electronic Variations of sp/sp(2) Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)X-2 (X = I, NCS) Moieties
Lissel Franziska, Blacque Olivier, Venkatesan Koushik, Berke Heinz (2015), Structural and Electronic Variations of sp/sp(2) Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)X-2 (X = I, NCS) Moieties, in ORGANOMETALLICS, 34(2), 408-418.
Break-junctions for investigating transport at the molecular scale.
Schwarz Florian, Lörtscher Emanuel (2014), Break-junctions for investigating transport at the molecular scale., in Journal of physics. Condensed matter : an Institute of Physics journal, 26(47), 474201-474201.
High-Conductive Organometallic Molecular Wires with De localized Electron Systems Strongly Coupled to Metal Electrodes
Schwarz Florian, Kastlunger Georg, Lissel Franziska, Riel Heike, Venkatesan Koushik, Berke Heinz, Stadler Robert, Loertscher Emanuel (2014), High-Conductive Organometallic Molecular Wires with De localized Electron Systems Strongly Coupled to Metal Electrodes, in NANO LETTERS, 14(10), 5932-5940.
Organometallic Single-Molecule Electronics: Tuning Electron Transport through X(diphosphine)(2)FeC4Fe(diphosphine)(2)X Building Blocks by Varying the Fe-X-Au Anchoring Scheme from Coordinative to Covalent
Lissel Franziska, Schwarz Florian, Blacque Olivier, Riel Heike, Loertscher Emanuel, Venkatesan Koushik, Berke Heinz (2014), Organometallic Single-Molecule Electronics: Tuning Electron Transport through X(diphosphine)(2)FeC4Fe(diphosphine)(2)X Building Blocks by Varying the Fe-X-Au Anchoring Scheme from Coordinative to Covalent, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(41), 14560-14569.
Impact of 2,6-connectivity in Azulene: Optical Properties and Stimuli Responsive Behavior
Koch Michael, Blacque Olivier, Venkatesan Koushik (2013), Impact of 2,6-connectivity in Azulene: Optical Properties and Stimuli Responsive Behavior, in Journal of Materials Chemistry C, 44(1), 7400-7408.
Dinuclear and Mononuclear Chromium Acetylide Complexes
Egler-Lucas C, Blacque O, Venkatesan K, Lopez-Hernandez A, Berke H (2012), Dinuclear and Mononuclear Chromium Acetylide Complexes, in EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (9), 1536-1545.
Syntheses and Tunable Emission Properties of 2-Alkynyl Azulenes
Koch Michael, Blacque Olivier, Venkatesan Koushik (2012), Syntheses and Tunable Emission Properties of 2-Alkynyl Azulenes, in Organic Letters, 14(6), 1580-1583.
An iron-capped metal-organic polyyne: {[Fe](C[triple bond]C)2[W][triple bond]CC[triple bond]CC[triple bond][W](C[triple bond]C)2[Fe]}.
Semenov Sergey N, Taghipourian Shiva F, Blacque Olivier, Fox Thomas, Venkatesan Koushik, Berke Heinz (2010), An iron-capped metal-organic polyyne: {[Fe](C[triple bond]C)2[W][triple bond]CC[triple bond]CC[triple bond][W](C[triple bond]C)2[Fe]}., in Journal of the American Chemical Society, 132(22), 7584-5.
Electronic Communication in Dinuclear C-4-Bridged Tungsten Complexes
Semenov SN, Blacque O, Fox T, Venkatesan K, Berke H (2010), Electronic Communication in Dinuclear C-4-Bridged Tungsten Complexes, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132(9), 3115-3127.

Collaboration

Group / person Country
Types of collaboration
University of Zürich Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
IBM Zürich Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
PD Dr. Robert Stadler Austria (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Control of Transport in Molecular Nanocontacts Talk given at a conference Electron Transport and Optics in Single-Molecule Nanocontacts 26.03.2015 Stuttgart, Germany Lörtscher Emanuel;
Controlled Charge and Heat Transport at the Molecular Scale Talk given at a conference Experimental Investigation of Single-­‐Molecule Junctions: Electron transport, thermopower and optics 29.09.2014 Konstanz, Germany Lörtscher Emanuel;
Department Seminar - University of Wisconsin-Madison Individual talk Rational Design Approaches to Electronic Materials 18.08.2014 Wisconsin, Madison, United States of America Venkatesan Koushik;
International Coordination Chemistry Conference- ICCC41 Talk given at a conference Rational Design Approaches to Highly Efficient Deep Blue Emitting Triplet Phosphors 20.07.2014 Singapore, Singapore Venkatesan Koushik;
International Conference on Nanoscience + Technology Talk given at a conference Redox-Active Organometallic Molecules for Future Memory Applications 20.07.2014 Denver, Colorado, United States of America Lörtscher Emanuel;
2014 MRS Spring Meeting & Exhibit Talk given at a conference Fabrication and Characterization of Resonant Bowtie Antennas with Tunable Gap Sizes below 5 nm for Simultaneous Detection of Singlemolecule Emission and Raman Scattering 21.04.2014 San Francisco, United States of America Lörtscher Emanuel;
12th European Conference on Molecular Electronics Poster Probing Electronic Properties through Specific Design of Organometallic Molecules 03.12.2013 London, Great Britain and Northern Ireland Lissel Franziska;
15th International Symposium on Novel Aromatic Compounds (ISNA) Poster Investigation of 2,6 connected azulene towards low-band gap materials 28.07.2013 Taipei, Taiwan Koch Michael;
European Conference on Molecular Electronics Poster Designing Organometallic Molecular Wires 03.07.2013 London, Great Britain and Northern Ireland Lissel Franziska;
Swiss Nanoconvention 2013 Poster Organometallic Molecules for Future Memory Applications 23.05.2013 Basel, Switzerland Lörtscher Emanuel;
6th International Meeting on Molecular Electronics Poster Organometallic Molecules for Future Memory Applications 03.12.2012 Grenoble, France Lörtscher Emanuel;
Annual meeting of NRP62 Individual talk Functional organic and organometallic materials for molecular electronic applications 15.09.2011 Fribourg, Switzerland Berke Heinz; Koch Michael;
European conference on Molecular Electronics Poster An Iterative Approach to Access Well‐defined Molecular Wires 07.09.2011 Barcelona, Spain Lissel Franziska;
NRP62 Kickoff meeting Individual talk Functional Organic and Organometallic Materials for Molecular Electronics 21.04.2010 Fribourg, Switzerland Berke Heinz;


Knowledge transfer events

Active participation

Title Type of contribution Date Place Persons involved
Technology Apero NRP62 14.09.2011 Fribourg, Switzerland Berke Heinz;


Awards

Title Year
2013 CMSZH Travel Award» sponsored by Büchi 2013
2013 CMSZH Travel Award» sponsored by Sigma Aldrich Chemie 2013
SCNAT Travel Award 2013

Abstract

This proposal aims at the design and development of novel organic and organometallic-based molecular wires for potential applications in molecular electronics utilizing a bottom-up approach. Synthesis and characterization of an elaborate array of rigid-rod wires based on manganese (Mn), rhenium (Re), Iron (Fe) and tungsten (W) with careful selection of appropriate conjugated organic bridges would be part of this work that would establish the transition metal and the bridge influence on the electronic properties of these molecular wires. These studies would help to make the right choice of the metal and the bridge in these rigid-rod wires for applications, which has been quite lacking in this field up to now. These molecules will be post-functionalized with sulfur end groups such these molecules can be attached on gold surfaces and further incorporate them into devices. In addition these new materials with interesting technological applications will not only be synthesized but also will be characterized by state of the art techniques that include structural determination, AFM/STM microscopies, magnetic measurements (dc and ac magnetic susceptibility), transport measurements (single molecule conduction) and other spectroscopic methods. IBM ZRL will characterize the electrical conductance of individual molecules and small ensembles of molecules using the mechanically controllable break-junction (MCBJ) technique. In this approach, the distance between two electrodes can be mechanically controlled with picometer resolution to adapt to the length of a single molecule, which can be captured in between. Using molecules with appropriate anchor groups (e.g. thiols), the MCBJ method allows for a reliable and durable chemical contact at both ends of the molecule to mimic the simplest two terminal device geometry. Systematic measurements and statistic analysis reveal the correlation between the molecular structure and electrical functionality of the molecule.
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