Show simple item record

dc.contributor.authorSENGE, MATHIAS
dc.date.accessioned2013-10-22T10:20:15Z
dc.date.available2013-10-22T10:20:15Z
dc.date.issued2011
dc.date.submitted2011en
dc.identifier.citationRyan, A.; Gehrold, A.; Peresutti, R.; Pintea, M.; Fazekas, M.; Locos, O. B.; Blaikie, F.; Senge, M. O., Synthesis of Unsymmetrical meso-Substituted Porphyrins, 2. Porphyrin Dimers and Arrays, European Journal of Organic Chemistry, n/a, 2011, 5817 5844en
dc.identifier.otherY
dc.identifier.urihttp://hdl.handle.net/2262/67529
dc.descriptionPUBLISHEDen
dc.description.abstractCurrent applications of porphyrins in medicine and optics, such as photodynamic therapy or nonlinear absorbers, increasingly require the use of far-red absorbing dyes. Modifications of the porphyrin structure to accommodate these conditions can be achieved by extending the conjugation of the porphyrin ?-system, which causes a bathochromic shift in the absorption spectrum. Thus, conjugated porphyrin oligomers have found widespread use. However, past synthetic strategies have mainly targeted symmetric porphyrin dimers, trimers, and oligomers which limit the practical use of such chromophores. Here, a series of symmetric and unsymmetric dimeric and trimeric porphyrin systems which are connected via conjugated linkers, namely alkyne and phenylacetylene, were synthesized via palladium catalyzed C-C coupling reactions. Adopting two approaches, firstly, a series of novel unsymmetric dimers was synthesized via the incorporation of all substituents on the monomeric components prior to coupling. The second was the synthesis of novel symmetric dimers and trimers with free meso positions enabling further chemistry to be carried out. The majority of these conjugated arrays exhibited a bathochromic shift in their UV/vis absorption, in particular the alkyne linked arrays which showed absorption greater than 720 nm. The mass spectrometry spectra for phenylacetylene and diphenylbutadiene linked zinc arrays exhibited detachment of zinc from the porphyrin core in their spectra. These unusual results are both linker and metal dependent, usually only seen for more labile metals.en
dc.description.sponsorshipThis work was supported by grants from Science Foundation Ireland (SFI P.I. 09/IN.1/B2650 and SFI Ureka Supplement 04/RP1/B482UR08) and the Health Research Board (HRB Translational Research Award 2007 TRA/2007/11). We are grateful to the Centre for Synthesis and Chemical Biology (CSCB) for HRMS measurements.en
dc.format.extent5817 5844en
dc.language.isoenen
dc.relation.ispartofseriesEuropean Journal of Organic Chemistry;
dc.relation.ispartofseriesn/a;
dc.rightsYen
dc.subject.otherPorphyrins
dc.titleSynthesis of Unsymmetrical meso-Substituted Porphyrins, 2. Porphyrin Dimers and Arraysen
dc.typeJournal Articleen
dc.type.supercollectionscholarly_publicationsen
dc.type.supercollectionrefereed_publicationsen
dc.identifier.peoplefinderurlhttp://people.tcd.ie/sengem
dc.identifier.rssinternalid78004
dc.rights.ecaccessrightsOpenAccess


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record