ISSN:
0009-2940
Keywords:
Zirconium porphyrins
;
Hafnium porphyrins
;
Porphyrin double deckers
;
Metal bisporphyrinates
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The synthesis of new zirconium and hafnium bisporphyrinate double deckers M(P)2 (M=Zr, Hf; P=OEP, TPP)2,3) is described. The complexes are characterized by UV/Vis/NIR and 1H-NMR spectroscopy and cyclic voltammetry. As compared with M=Ce, the redox potentials or the energies of the nearinfrared absorption bands of the corresponding radical cations [M(P)2]+ are lower by ≍ 0.2 V or higher by ≍ 2000 cm-1, respectively, Hence, there is a stronger π-π interaction between the porphyrin ligands as compared with the cerium analogues due to the smaller ionic radii of Zr(IV) and Hf(IV). X-ray crystallography of Zr(TPP)2 confirms the sandwich-like structure of the compound and the close proximity of the porphyrin ligands.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240511
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