uu.seUppsala University Publications
Change search
ReferencesLink to record
Permanent link

Direct link
Tuning of Photocatalytic Hydrogen Production and Photoinduced Intramolecular Electron Transfer Rates by Regioselective Bridging Ligand Substitution
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Molecular Biomimetics.
Show others and affiliations
2011 (English)In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 12, no 11, 2101-2109 p.Article in journal (Refereed) Published
Abstract [en]

Artificial photosynthesis based on supramolecular photocatalysts offers the unique possibility to study the molecular processes underlying catalytic conversion of photons into chemical fuels in great detail and to tune the properties of the photocatalyst by alterations of the molecular framework. Herein we focus on both possibilities in studying the photocatalytic reduction of protons by derivatives of the well-known photocatalyst [(tbbpy)(2)Ru(tpphz)PdCl(2)](PF(6))(2) [4,4'-di-tert-butyl-2,2'-bipyridine (tbbpy), tetrapyrido[3,2-a:2',3'-c:3 '',2 ''-h:2'", 3'"-j]phenazine (tpphz)]. We report on a modified photocatalyst where the crucial bridging ligand tpphz is substituted by bromine and investigate the effect of the structural variation on the catalytic properties of the complex and its ultrafast intramolecular charge transfer behavior. It is found that structural modification stabilizes the phenanthroline-centered metal-to-ligand charge-transfer state on the tpphz moiety, thereby reducing the electron transfer gradient across the entire electron-relaying bridging ligand and at the same time accelerating nanosecond ground-state recovery. The same structural modifications cause an overall reduction of the catalytic activity of the complex. Thus, the results highlight the potential of small structural variations in the molecular framework of supramolecular catalysts in understanding the photoinduced charge-transfer processes and optimizing their catalytic performance.

Place, publisher, year, edition, pages
2011. Vol. 12, no 11, 2101-2109 p.
Keyword [en]
hydrogen, photocatalysis, photochemistry, supramolecular chemistry, time-resolved spectroscopy
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-157252DOI: 10.1002/cphc.201100245ISI: 000293385400009OAI: oai:DiVA.org:uu-157252DiVA: diva2:436387
Available from: 2011-08-23 Created: 2011-08-22 Last updated: 2011-08-23Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text
By organisation
Molecular Biomimetics
In the same journal
Natural Sciences

Search outside of DiVA

GoogleGoogle Scholar
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

Altmetric score

Total: 423 hits
ReferencesLink to record
Permanent link

Direct link