Project

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Sustainable nanoscale and materials chemistry

Applicant Constable Edwin Charles
Number 144500
Funding scheme Project funding (Div. I-III)
Research institution Institut für Anorganische Chemie Departement Chemie Universität Basel
Institution of higher education University of Basel - BS
Main discipline Inorganic Chemistry
Start/End 01.10.2012 - 30.09.2015
Approved amount 589'938.00
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Keywords (5)

Sustainable; Complexes; Photovoltaic; Water splitting; Light emitting electrochemical cell

Lay Summary (English)

Lead
Lay summary

This project relates to the development of a sustainable and low-tech materials chemistry. The target technologies involve photonic devices which either absorb light and convert light energy to electrical energy (photovoltaic devices) or convert electrical energy to light (light emitting electrochemical cells or OLEDs). The aim is to replace expensive and rare elements such as ruthenium and iridium which are critical to todays state of the art devices by cheaper and Earth abundant metals.

In parallel, low tech approaches to light/photon initiated data storgae are being investigated with a long term view to coupling the above technologies in an intelligent curtain, which can absorb light during the day and emit light at night.

Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
[Ir(C^N)2(N^N)]+ emitters containing a naphthalene unit within a linker between the two cyclometallating ligands
Bünzli Andreas M, Pertegás Antonio, Momblona Cristina, Junquera-Hernández José M, Constable Edw (2016), [Ir(C^N)2(N^N)]+ emitters containing a naphthalene unit within a linker between the two cyclometallating ligands, in Dalton Transactions, 45, 16379 - 16392.
Improving performance of copper(I)-based dye sensitized solar cells through I3–/I– electrolyte manipulation
Fürer S. O., Luu L. Y. N., Bozic-Weber B., Constable E. C., Housecroft C. E. (2016), Improving performance of copper(I)-based dye sensitized solar cells through I3–/I– electrolyte manipulation, in Dyes Pigments, 132, 72-78.
Regioisomerism in cationic sulfonyl-substituted [Ir(C^N)2(N^N)]+ complexes: its influence on photophysical properties and LEC performance
Ertl Cathrin D, Gil-Escrig Lidón, Cerdá Jesús, Pertegás Antonio, Bolink Henk J, Junquera-Hernán (2016), Regioisomerism in cationic sulfonyl-substituted [Ir(C^N)2(N^N)]+ complexes: its influence on photophysical properties and LEC performance, in Dalton Transactions, 45, 11668-11681.
Colour tuning by the ring roundabout: [Ir(C^N)2(N^N)]+ emitters with sulfonyl-substituted cyclometallating ligands
ErtlC.D. CerdáJ. Junquera-HernándezJ. PertegásA. BolinkH.J. ConstableE.C. ……HousecroftC.E. (2015), Colour tuning by the ring roundabout: [Ir(C^N)2(N^N)]+ emitters with sulfonyl-substituted cyclometallating ligands, in RSC Advances, 5, 42815- 42827.
Copper(I)-based dye-sensitized solar cells with sterically demanding anchoring ligands: bigger is not always better
Brauchli S.Y. MalznerF.J.Constable E.C. Housecroft C.E. (2015), Copper(I)-based dye-sensitized solar cells with sterically demanding anchoring ligands: bigger is not always better, in RSC Advances, 5, 48516-48525.
Sticking and patching: tuning and anchoring cyclometallated ruthenium(II) complexes
Ertl C.D. RisD.P. MeierS.C. ConstableE.C. HousecroftC.E. Neuburger M. Zampese J. A. (2015), Sticking and patching: tuning and anchoring cyclometallated ruthenium(II) complexes, in Dalton Trans., 44, 1557 - 1570.
The beneficial effects of trifluoromethyl-substituents on the photoconversion efficiency of copper(I) dyes in dye-sensitized solar cells
BrunnerF. KleinM. KellerS. MorrisC.D. PrescimoneA. Constable E.C. HousecroftC.E. (2015), The beneficial effects of trifluoromethyl-substituents on the photoconversion efficiency of copper(I) dyes in dye-sensitized solar cells, in RSC Adv., 5, 58694-58703.
Assembling model tris(bipyridine)ruthenium(II) photosensitizers into ordered monolayers in the presence of the polyoxometallate anion [Co4(H2O)2(α-PW9O34)2]10–
MurrayN. RuddJ.A. ChamayouA. ConstableE.C. HousecroftC.E. Neuburger M. Zampese J (2014), Assembling model tris(bipyridine)ruthenium(II) photosensitizers into ordered monolayers in the presence of the polyoxometallate anion [Co4(H2O)2(α-PW9O34)2]10–, in RSC Advances, 4, 11766 - 11775.
Chloride ion impact on materials for light-emitting electrochemical cells
SchneiderG. BolinkH. ConstableE.C. ErtlC.D. HousecroftC.E. PertegasA. Za…. (2014), Chloride ion impact on materials for light-emitting electrochemical cells, in Dalton Trans., 43, 1961-1964.
Green-emitting iridium(III) complexes containing sulfone-functionalized cyclometallating 2-phenylpyridine ligands
Constable E.C. Ertl C.D. Housecroft C.E. Zampese J.A. (2014), Green-emitting iridium(III) complexes containing sulfone-functionalized cyclometallating 2-phenylpyridine ligands, in Dalton Trans., 43, 5343-5356.
Halos show the path to perfection: peripheral iodo-substituents improve the efficiencies of bis(diimine)copper(I) dyes in dye-sensitized solar cells
Malzner F.J. Brauchli S.Y. ConstableE.C. Housecroft C.E. Neuburger M. (2014), Halos show the path to perfection: peripheral iodo-substituents improve the efficiencies of bis(diimine)copper(I) dyes in dye-sensitized solar cells, in RSC Advances, 4, 48712-48723.
Influence of a co-adsorbent on the performance of bis(diimine) copper(I)-based dye-sensitized solar cells
Brauchli S.Y. MalznerF. J. Constable E.C. Housecroft C.E. (2014), Influence of a co-adsorbent on the performance of bis(diimine) copper(I)-based dye-sensitized solar cells, in RSC Advances, 4, 62728 - 62736.
Phosphonate-functionalized heteroleptic ruthenium(II) bis(2,2':6',2''-terpyridine) complexes
ConstableE.C. HousecroftC.E. Šmídková M. Zampese J. A. (2014), Phosphonate-functionalized heteroleptic ruthenium(II) bis(2,2':6',2''-terpyridine) complexes, in Can. J. Chem, 92, 724-730.
To deprotect or not to deprotect: phosphonate ester versus phosphonic acid anchor ligands in copper(I)-based dye-sensitized solar cells
MalznerF.J.Brauchli S. Schönhofer E. Constable E.C. Housecroft C.E. (2014), To deprotect or not to deprotect: phosphonate ester versus phosphonic acid anchor ligands in copper(I)-based dye-sensitized solar cells, in Polyhedron, 82, 116-121.
Bis(4'-(4-pyridyl)-2,2':6',2"-terpyridine)ruthenium(II) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation
Lv H.Rudd J.A. Zhuk P. Lee J.Y. Constable E.C. Housecroft C.E. Hill C. Musae D….. (2013), Bis(4'-(4-pyridyl)-2,2':6',2"-terpyridine)ruthenium(II) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation, in RSC Advances, 3, 20647-20654.
Improving the photoresponse of copper(I) dyes in dye-sensitized solar cells by tuning ancillary and anchoring ligand modules
Bozic-Weber B. Brauchli S.Y. Constable S. O. Fürer E.C. Housecroft C.E. Malzner F.J. Wright I (2013), Improving the photoresponse of copper(I) dyes in dye-sensitized solar cells by tuning ancillary and anchoring ligand modules, in Dalton Trans., 42, 12293- 12308.
Light harvesting with Earth abundant d-block metals: towards a sustainable materials chemistry
Bozic-WeberB. Constable E.C. Housecroft C.E. (2013), Light harvesting with Earth abundant d-block metals: towards a sustainable materials chemistry, in Coord. Chem. Rev., 257, 3089- 3106.
Exploring copper(I)-based dye-sensitized solar cells: a complementary experimental and TD-DFT investigation
Bozic-WeberB. ChaurinV. ConstableE.C. HousecroftC.E. MeuwlyM. NeuburgerM. Rudd J.A. (2012), Exploring copper(I)-based dye-sensitized solar cells: a complementary experimental and TD-DFT investigation, in Dalton Trans., 41, 14157- 14169.
4'-Functionalized 2,2':6',2''-terpyridines as the N^N domain in [Ir(C^N)2(N^N)][PF6] complexes
RisD. SchneiderG. ErtlC.D. KohlerE. MüntenerT. NeuburgerM.Constable E.C. Housecroft C.E., 4'-Functionalized 2,2':6',2''-terpyridines as the N^N domain in [Ir(C^N)2(N^N)][PF6] complexes, in J. Organomet. Chem..
The Emergence of copper(I)-based dye sensitized solar cells
Constable E.C. Housecroft C.E., The Emergence of copper(I)-based dye sensitized solar cells, in Chem Soc. Rev.

Collaboration

Group / person Country
Types of collaboration
Prof. Craig Hill, Emory University United States of America (North America)
- Publication
Dr Ermst Meyer, Universität Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Dr Alberto Credi, University of Bologna Italy (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Exchange of personnel
Prof. Silvio Decurtins, Universität Bern Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
Dr. Cornelia Paliva, Universität Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
Dr Henk Bolink, University of Valencia Spain (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Dr Artur Braun, EMPA, Dubendorf Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Associated projects

Number Title Start Funding scheme
132498 Applied supramolecular and nanoscale chemistry 01.10.2010 Project funding (Div. I-III)
162631 Materials chemistry and sustainable energy 01.10.2015 Project funding (Div. I-III)
157777 High-end X-ray diffraction instrumentation for chemical crystallography 01.06.2015 R'EQUIP
157687 Picosecond Transient Absorption Setup for Detection of Short-Lived Photoproducts and Excited States in Molecular Systems 01.11.2015 R'EQUIP
132498 Applied supramolecular and nanoscale chemistry 01.10.2010 Project funding (Div. I-III)

Abstract

One of the major challenges facing mankind in the next Century is the transition from fossil fuels as the primary energy source to alternative generation methods. In addition there is a demand for more efficient usage of existing energy sources. Materials and nanoscale science have made enormous advances in developing, at least to the proof-of-principle stage, technologies that can address the scientific issues. Unfortunately, many of the emerging technologies are based upon elements which are scarce, rendering the long-term sustainability questionable.This proposal concerns a variety of sub-projects related to the development of (i) energy efficient lighting devices (LECs) based on iridium or earth abundant metals (ii) sustainable dye-sensitized solar cells (DSCs) based on copper and (iii) functionalised interfaces.Light-emitting electrochemical cells (LECs) are simple and cost-effective devices related to OLEDs. State-of-the-art devices use iridium complexes. We are developing new complexes for long-lived LECs using strategies based on variation of ligand structure to tune the emission maxima. The complexes will incorporate the features we have already shown to lead to long-lived devices. We will also investigate the use of copper(I) and zinc(II) complexes incorporating bidentate diimines and bidentate soft PP, PS and SS donors. To date, there have only been very few examples of LECs based on first row transition metals. We will further develop a high throughput method of testing luminescent compounds for use in LECs.We recently described the first examples of efficient DSCs using copper(I) complexes as sensitizers. Following this first result we have worked on improving the efficiencies of these devices. We are now further increasing our effort in designing complexes for copper(I)-DSCs to maintain our world-leading position. We have recently prepared DSCs with efficiencies of the order of 7%. We will also develop exchange reactions for the construction of optimized DSCs and DSCs with libraries of complexes, avoiding the need to design "black" dyes.Finally, we will extend our studies on photocatalytic systems for the oxidation of water to heterogeneous systems and possibly to tandem cells. In particular, we will use functional multilayers prepared from Langmuir Blodgett films of cationic, photoactive luminescent complexes on aqueous sub-layers of polyoxometallate clusters (the water oxidation catalysts).
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