Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Conducting Polymers Containing In-Chain Metal Centres: Electropolymerisation and Charge Transport
Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Physical Chemistry.
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Conjugated polymers that exhibit high electronic conductivities play key roles in the emerging field of molecular electronics. In particular, linking metal centres with useful electrochemical, photophysical, or catalytic properties to the backbone, or within the polymer chain itself, is a topic which has attracted a significant amount of interest lately. Structurally rigid monomers that can be electropolymerised to form highly conducting molecular wires may provide new insights into conduction mechanisms, e.g., exploiting resonant superexchange (electron-hopping) by tuning the energies of redox centre and bridge states. The focus of this thesis lies on the electrochemical investigation of preparation, growth dynamics, and charge transport dynamics of oligothiophene/transition metal hybrid materials. The incorporation of ruthenium(II) and osmium(II) terpyridine complexes into such polymeric assemblies was accomplished by an electropolymerisation procedure, to produce rod-like oligothienyl-bridged metallopolymers. The properties of the monomers used were characterised by optical spectroscopy and electrochemical techniques. Charge transport was studied in detail for some of the materials created, and it was found that the electron transport rate and dc conductivity was enhanced by up to two orders of magnitude compared to relevant non-conjugated polymers, demonstrating the usefulness of this approach for optimization of charge transport in metallopolymers. The charge transport diffusion coefficent was determined to (2.6 ± 0.5) x 10-6 cm2 s-1 for a quaterthienyl-bridged {Os(tpy)2} polymer by use of an electrochemical steady-state method carried out using a transistor-like experimental geometry. It was found that charge transport in these materials is concentration-gradient driven. The rate limiting step of the charge transport process was investigated using electrochemical impedance spectroscopy. The electropolymerisation dynamics of one of the monomers was studied using microelectrodes, and the results obtained shows that electropolymerisation is highly efficient, and indicate that mass transport controls this process. Through a combination of controlled potential deposition and SEM imaging it was demonstrated that it is possible to exploit the edge effect of microelectrodes to promote film growth in a direction co-planar with the electrode surface.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2003. , p. 65
Series
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1104-232X ; 910
Keywords [en]
Physical chemistry, Polymer electrochemistry, Conducting Polymers, Metal Complexes, Electropolymerization, Electron-hopping, Microelectrodes
Keywords [sv]
Fysikalisk kemi
National Category
Physical Chemistry
Research subject
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-3789ISBN: 91-554-5813-0 (print)OAI: oai:DiVA.org:uu-3789DiVA, id: diva2:163712
Public defence
2003-12-12, B42, BMC, Husarg. 3, Uppsala, 10:15
Opponent
Supervisors
Available from: 2003-11-13 Created: 2003-11-13Bibliographically approved
List of papers
1. Electropolymerisable bipyridine ruthenium(II) complexes. Synthesis and electrochemical characterisation of 4-(3-methoxystyryl)- and 4,4'-di(3-methoxystyryl)-2,2'-bipyridine ruthenium complexes
Open this publication in new window or tab >>Electropolymerisable bipyridine ruthenium(II) complexes. Synthesis and electrochemical characterisation of 4-(3-methoxystyryl)- and 4,4'-di(3-methoxystyryl)-2,2'-bipyridine ruthenium complexes
2001 In: Journal of the Chemical Society - Dalton Transactions, ISSN 1472-7773, no 8, p. 1319-1325Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-91106 (URN)
Available from: 2003-11-13 Created: 2003-11-13 Last updated: 2011-04-06
2. A rod-like polymer containing {Ru(terpy)2} units prepared by electrochemical coupling of pendant thienyl moieties
Open this publication in new window or tab >>A rod-like polymer containing {Ru(terpy)2} units prepared by electrochemical coupling of pendant thienyl moieties
Show others...
2002 (English)In: Chemical Communications, ISSN 1359-7345, no 3, p. 284-285Article in journal (Refereed) Published
Abstract [en]

A new rod-like coordination polymer consisting of (Ru-(terpy)2) motifs bridged by bithiophene units has been prepared by electrochemical polymerisation in acidic organic medium. 

Identifiers
urn:nbn:se:uu:diva-91107 (URN)
Available from: 2003-11-13 Created: 2003-11-13 Last updated: 2011-04-19
3. Conducting polymers containing in-chain metal centers: Homogeneous charge transport through a quaterthienyl-bridged {Os(tpy)2} polymer
Open this publication in new window or tab >>Conducting polymers containing in-chain metal centers: Homogeneous charge transport through a quaterthienyl-bridged {Os(tpy)2} polymer
Show others...
2003 In: Journal of Physical Chemistry B, ISSN 1520-6106, Vol. 107, no 38, p. 10431-10439Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-91108 (URN)
Available from: 2003-11-13 Created: 2003-11-13 Last updated: 2011-04-06
4. Electropolymerisation dynamics of a highly conducting metallopolymer: Poly-[Os(4'-(5-(2,2'-bithienyl))-2,2':6',2''-terpyridine)2]2+
Open this publication in new window or tab >>Electropolymerisation dynamics of a highly conducting metallopolymer: Poly-[Os(4'-(5-(2,2'-bithienyl))-2,2':6',2''-terpyridine)2]2+
Show others...
In: Article in journal (Refereed) Submitted
Identifiers
urn:nbn:se:uu:diva-91109 (URN)
Available from: 2003-11-13 Created: 2003-11-13 Last updated: 2011-04-06
5. Conducting polymers containing in-chain metal centers: Electropolymerization of oligothienyl-substituted {M(tpy)2} complexes and in-situ conductivity studies, M = Os(II), Ru(II)
Open this publication in new window or tab >>Conducting polymers containing in-chain metal centers: Electropolymerization of oligothienyl-substituted {M(tpy)2} complexes and in-situ conductivity studies, M = Os(II), Ru(II)
Show others...
2005 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 44, no 4, p. 1073-1081Article in journal (Refereed) Published
Abstract [en]

The electropolymerization of a series of Ru and Os bis-terpyridine complexes that form rodlike polymers with bithienyl, quaterthienyl, or hexathienyl bridges has been studied. Absorption spectroscopy, scanning electron microscopy, and cyclic voltammetry have been used to characterize the monomers and resulting polymer films. The absolute dc conductivity of the quaterthienyl-bridged {Ru(tpy)2} and {Os(tpy)2} polymers is unusually large and independent of the identity of the metal center at 1.6 × 10-3 S cm-1. The maximum conductivity occurs at the formal potential of each redox process, which typically is observed for systems where redox conduction is the dominant charge transport mechanism. Significantly, the dc conductivity of the metal-based redox couple observed in these polymers is 2 orders of magnitude higher than that of a comparable nonconjugated system.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-91110 (URN)DOI: 10.1021/ic049221m (DOI)
Available from: 2003-11-13 Created: 2003-11-13 Last updated: 2017-12-14

Open Access in DiVA

fulltext(1017 kB)4277 downloads
File information
File name FULLTEXT01.pdfFile size 1017 kBChecksum MD5
eaa7bcf9318eaf765582daf0bab368df9aca3f769e8903da8888e717095f342e5e824464
Type fulltextMimetype application/pdf
Buy this publication >>

By organisation
Department of Physical Chemistry
Physical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 4277 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 1364 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf