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Issue 24, 2014
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Constructing bis(porphyrinato) rare earth double-decker complexes involving N-confused porphyrin

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Abstract

Reaction of metal-free N-confused 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (H2NTClPP) with metal-free 5,10,15,20-tetrakis[(4-tert-butyl)phenyl]porphyrin (H2TBPP) in the presence of MIII(acac)3·nH2O (acac = acetylacetonate) in refluxing 1,2,4-trichlorobenzene (TCB) led to the isolation of heteroleptic bis(porphyrinato) rare earth compounds MIII(HNTClPP)(TBPP) (M = La, Pr) (1, 2) in 6.7–10% yield. These represent the first examples of sandwich-type porphyrin rare earth double-decker complexes that involve N-confused porphyrin ligand. Different from their homoleptic bis(porphyrinato) rare earth double-decker counterparts HMIII(TBPP)2 (M = La, Pr) (3, 4), the acidic proton in the heteroleptic analogues was revealed to localize at the inverted pyrrole nitrogen atom of the N-confused porphyrin ligand on the basis of NMR spectroscopic studies. Nevertheless, their heteroleptic bis(porphyrinato) sandwich molecular nature was confirmed on the basis of single crystal X-ray diffraction analysis over the praseodymium double-decker complex.

Graphical abstract: Constructing bis(porphyrinato) rare earth double-decker complexes involving N-confused porphyrin

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Publication details

The article was received on 21 Jan 2014, accepted on 21 Mar 2014 and first published on 24 Mar 2014


Article type: Paper
DOI: 10.1039/C4DT00216D
Citation: Dalton Trans., 2014,43, 9152-9157
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    Constructing bis(porphyrinato) rare earth double-decker complexes involving N-confused porphyrin

    Y. Zhang, W. Cao, K. Wang and J. Jiang, Dalton Trans., 2014, 43, 9152
    DOI: 10.1039/C4DT00216D

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