http://dx.doi.org/10.1002/ejic.200800267">
 

Document Type

Journal Article

Department/Unit

Department of Chemistry

Title

Synthesis, structure and spectroscopic properties of lanthanide complexes of N-confused porphyrins

Language

English

Abstract

A series of meso-substituted N-confused porphyrins (NCP) is synthesized using the modified Rothemund-Lindsey procedure. Lanthanide N-confused porphyrinate complexes of the general formula [(NCP)Ln(LOMe)] [Ln3+ = Yb3+ and Er3+; LOMe- = (η5-C5H5)Co{P(=O)(OMe)2} 3 -] are obtained in moderate yields upon interaction of N-confused porphyrin free bases (H2NCP) with Ln[N(SiMe 2)3]·x[LiCl(THF)3], followed by the addition of the tripodal anion LOMe- as an effective encapsulating agent for the lanthanide ions. The structural and spectroscopic data for these complexes provide evidence for an η2-agostic interaction between the Ln3+ ion and the inner C-H bond of the NCP ligand. Methylation of [(NCTCPP)Yb(LOMe)] (H2NCTCPP = 2-azo-5,10,15,20- tetracyanophenyl-21-carbaporphyrin) with methyl iodide yields the novel stable lanthanide complex of the N-methylated derivative of N-confused porphyrins, whose X-ray structure also exhibits an η2-agostic interaction between the metal center and the inner C-H bond of the NCTCPP ligand. The photophysical properties of the N-confused porphyrins and their lanthanide complexes are investigated. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Keywords

Agostic interactions, Fluorescence, Lanthanides, N ligands, Porphyrinoids

Publication Date

2008

Source Publication Title

European Journal of Inorganic Chemistry

Volume

2008

Issue

20

Start Page

3151

End Page

3162

Publisher

Wiley-VCH Verlag

ISSN (print)

14341948

ISSN (electronic)

10990682

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