Project

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Assembly of organometallic components for electronic and magnetic applications

English title Assembly of organometallic components for electronic and magnetic applications
Applicant Albrecht Martin
Number 121855
Funding scheme Project funding (Div. I-III)
Research institution School of Chemistry and Chemical Biology University College Dublin
Institution of higher education University of Fribourg - FR
Main discipline Inorganic Chemistry
Start/End 01.10.2008 - 30.09.2011
Approved amount 401'934.15
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All Disciplines (2)

Discipline
Inorganic Chemistry
Organic Chemistry

Keywords (9)

organometallics; metal-metal interactions; heterocyclic carbenes; redox activity; spin crossover; self-assembly; redox-activity; molecular wires; semiconductor materials

Lay Summary (English)

Lead
Lay summary
Based on our previous studies, we propose the use of transition metal carbene complexes as redox-active entities for the construction of materials for application in molecular electronics. Our studies have shown that in iron(II) and ruthenium(II) carbene complexes, the pi contribution to the metal-carbene bond may be significant, and that electronic coupling of two metal centers through a metal-carbene bond is efficient. In addition, carbene ligands have a great potential in molecular electronics, since they combine a variety of advantageous properties: strong metal complexation through covalent bonding minimizes metal leaching, ligand tuning through wingtip substitution allows to adjust the electronic properties of the active site, and ligand functionalization provides an effective methodology for introducing secondary properties such as recognition sites for controlled assembly. We propose to achieve our goals via a multi-centered approach: First, we will focus on the self-assembly of magnetically and/or electronically active components in solution and mono- amd multilayer films. These efforts are expected to provide a detailed understanding on the crucial effects to be considered for fabricating functional materials. Specifically, we will concentrate on the functionalization of complexes that are known to undergo reversible spin crossover and/or redox activity by attaching molecular recognition sites. Second, we aim at exploiting the unique properties of NHC complexes developed in our laboratories for self-assembly and for the construction of electronically active materials. Bimetallic carbene complexes are excellent components for such purposes, since they have been shown to impart intriguing properties as electronically coupled redox-switches. Third, new carbene-type complexes will be developed based on pyridinium-derived carbenes as ligands for coordinating spin- and/or redox-active metal centers. Pyridylidenes are particularly attractive ligands for electronic applications because synthetic variations are vast and well-described, and because their covalent metal-carbon bond can be tuned effectively. A common goal to all these subprojects is the exploitation of lateral metal-metal interactions. Electronically and/or magnetically active materials will then be accessible by using a hierarchically organizing the active components, thus linking the well-developed structural aspects of self-assembly with the rational extrapolation of functionality from molecular systems to devices for macroscopic application.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Abnormal N-Heterocyclic Carbene Palladium Complexes: Synthesis, Structure, and Reactivity
A. Poulain M. Iglesias M. Albrecht (2011), Abnormal N-Heterocyclic Carbene Palladium Complexes: Synthesis, Structure, and Reactivity, in Curr. Org. Chem., 15, 3325-3336.
Modulating the Steric, Electronic and Catalytic Properties of Cp* Ruthenium Half-sandwich Complexes with β-diketiminato Ligands
A. D. Phillips et al. (2011), Modulating the Steric, Electronic and Catalytic Properties of Cp* Ruthenium Half-sandwich Complexes with β-diketiminato Ligands, in Organometallics, 30, 6119-6132.
Probing Intermetallic Coupling in Dinuclear N-Heterocyclic Carbene Ruthenium(II) Complexes
L. Mercs A. Neels H. Stoeckli-Evans M. Albrecht (2011), Probing Intermetallic Coupling in Dinuclear N-Heterocyclic Carbene Ruthenium(II) Complexes, in Inorg. Chem., 50, 8188-8196.
Synthesis and Catalytic Activity of Histidine-based NHC Ruthenium Complexes
A. Monney G. Venkatachalam M. Albrecht (2011), Synthesis and Catalytic Activity of Histidine-based NHC Ruthenium Complexes, in Dalton Trans., 40, 2716-2719.
Synthesis and Self-Assembly of Spin-Labile and Redox-Active Manganese(III) Complexes
C. Gandolfi T. Cotting P. N. Martinho O. Sereda A. Neels G. G. Morgan M. Albrecht (2011), Synthesis and Self-Assembly of Spin-Labile and Redox-Active Manganese(III) Complexes, in Dalton Trans., 40, 1855-1865.
Synthesis and Tunability of Abnormal 1,2,3-Triazolylidene Palladium and Rhodium Complexes
Poulain A. et al. (2011), Synthesis and Tunability of Abnormal 1,2,3-Triazolylidene Palladium and Rhodium Complexes, in Organometallics, 30, 1021-1029.
[Ru(bpy)3]2+ Analogues Containing an N-heterocyclic Carbene Ligand
Ghattas W. Müller-Bunz H. Albrecht M. (2010), [Ru(bpy)3]2+ Analogues Containing an N-heterocyclic Carbene Ligand, in Organometallics, 29, 6782-6789.
Circular Polarized Lanthanide Luminescence from Langmuir-Blodgett Films Formed from Optically Active and Amphiphilic Eu(III) Based Self-Assembly Complexes
J. Kitchen D. Barry L. Mercs M. Albrecht R. Peacock T. Gunnlaugsson, Circular Polarized Lanthanide Luminescence from Langmuir-Blodgett Films Formed from Optically Active and Amphiphilic Eu(III) Based Self-Assembly Complexes, in Angew. Chem. Int. Ed., 51.
N-Heterocyclic Carbene Bonding to Cobalt Porphyrin Complexes
M. Albrecht P. Maji C. Häusl A. Monney H. Müller-Bunz, N-Heterocyclic Carbene Bonding to Cobalt Porphyrin Complexes, in Inorg. Chim. Acta.
Palladium Carbene Complexes for Selective Olefin Di- and Oligomerization
V. Khlebnikov et al., Palladium Carbene Complexes for Selective Olefin Di- and Oligomerization, in Organometallics, 31.
Tunable Spin-Crossover of Amphiphilic Iron(III) Complexes in Solution
C. Gandolfi G. G. Morgan M. Albrecht, Tunable Spin-Crossover of Amphiphilic Iron(III) Complexes in Solution, in Dalton Trans, 41.

Collaboration

Group / person Country
Types of collaboration
University of Trieste Italy (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
University College Dublin Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
EuCOMC Organometallic Chemistry Conference Talk given at a conference Ligand-Assisted Bond Activation by Metal Complexes Containing Strongly Mesoionic Carbenes 06.07.2011 Toulouse (France), France Albrecht Martin; Monney Angèle;
Innovation V, COST meeting Talk given at a conference Transfer and Direct Hydrogenation Using N-Heterocyclic Carbene Ruthenium Precursors 15.06.2011 La Valetta (Malta), Malta Khlebnikov Vsevolod; Albrecht Martin;
EuCheMS Inorganic Chemistry Conference Talk given at a conference Challenging the Norm: Catalytic Impact of Abnormal Carbene Ligands 13.04.2011 Manchester, UK, Great Britain and Northern Ireland Albrecht Martin;
RSC Workshop on Multifunctional Materials Talk given at a conference Supramolecular Tailoring of Magnetic Properties 01.04.2011 Dublin, IE, Ireland Khlebnikov Vsevolod; Albrecht Martin;
Pacifichem Talk given at a conference Challenging the Norm: Impact of Abnormal Carbene Ligands in Transition Metal Chemistry and Catalysis 16.12.2010 Honolulu, HI, United States of America Albrecht Martin;


Communication with the public

Communication Title Media Place Year
Media relations: print media, online media Forging ahead with metals to boost green energy UCD Today International 2011

Associated projects

Number Title Start Funding scheme
112703 Cooperatively operating hierachically organised materials for spintronics 01.02.2006 ERA-Chemistry
113547 Probing molecular electronics with organometallic components: From molecular switches to electronic devices 01.10.2006 Project funding (Div. I-III)

Abstract

Based on our previous studies, we propose the use of transition metal carbene complexes as redox-active entities for the construction of materials for application in molecular electronics. Our studies have shown that in iron(II) and ruthenium(II) carbene complexes, the pi contribution in the metal-carbene bond can be significant, and that electronic coupling of two metal centers through a metal-carbene bond is highly efficient. In addition, carbene ligands have a great potential in molecular electronics, since they combine a variety of advantageous properties: strong metal complexation through covalent bonding minimizes metal leaching, ligand tuning through wingtip substitution allows to adjust the electronic properties of the active site, and ligand functionalization provides an efficient methodology for introducing secondary properties such as recognition sites for controlled assembly. We propose to achieve our goals via a multicentered approach: Project A will focus on the self-assembly of magnetically and/or electronically active components in solution and in Langmuir-Blodgett films. This project encompasses the functionalization of organometallic and coordination complexes that are known to undergo reversible spin crossover and/or redox activity by attaching molecular recognition sites. Ideally, both magnetic and electronic transitions are combined in a single active site, thus allowing for addressing different states by orthogonal techniques (e.g. temperature and potential). A particular emphasis will be directed towards the factors that govern the stability and the structure of the self-assembled material (size of spherical particles in solution, Y- vs. Z-type LB multilayers). In addition, the effects of hierarchical organization will be probed by fabricating multilayered films in a controlled manner, for example by layer-by-layer assembly of the active components. These efforts together with dilution studies are expected to provide a detailed understanding on the crucial effects to be considered for fabricating nano- and microsize functional materials.Project B aims at exploiting the unique properties of NHC complexes developed in our laboratories for self-assembly and for the construction of more efficient materials. Bimetallic carbene complexes are excellent components for electronic applications, as they have been shown to impart tunable electronic properties such as bimetallic switching, isolating behavior, and tunable metal-carbene conductivity. These unique features will be used to create materials via (self-)assembly, either into monolayers (SAMs) and multilayers, or into coordination networks. Various methods are proposed for both types of assembly to evaluate and control metal-metal interactions, thus providing a rational for tuning the macroscopic properties of the functional material.Project C is devoted to the development of new carbene-type complexes that will highly suitable as new and tunable active sites. Specifically, we aim at using pyridinium-derived carbenes as ligands for coordinating redox-active ruthenium and spin- and redox-active iron and cobalt centers. Pyridylidenes are particularly useful for these applications because synthetic variations are vast and well-described, and because their (partially) covalent metal-carbon bond can be tuned effectively. Organometallic analogs of chelating 2,2’-bipyridine and 2,2’:6’,2’’ terpyridine are expected to provide excellent synthons for self-assembly, both via functionalization for LB-assembly into mono- and mulitlayers as well as for the construction of networks via manipulation of the residual metal coordination sites or functional sites at the chelate. A common goal to all these projects is the exploitation of lateral metal-metal interactions. Electronically and/or magnetically active materials will then be accessible by using a hierarchically organizing the active components, thus linking the well-developed structural aspects of self-assembly with the rational extrapolation of functionality from molecular systems to devices for macroscopic application.
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