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Heteroleptic Rare Earth Double‐Decker Complexes with Porphyrinato and 2,3‐Naphthalocyaninato Ligands − Preparation, Spectroscopic Characterization, and Electrochemical Studies
Author(s) -
Jiang Jianzhuang,
Liu Wei,
Cheng KaLok,
Poon KaWo,
Ng Dennis K. P.
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200102)2001:2<413::aid-ejic413>3.0.co;2-q
Subject(s) - chemistry , electrochemistry , metal , tetra , ionic bonding , ion , metal ions in aqueous solution , stereochemistry , redox , rare earth , crystallography , medicinal chemistry , inorganic chemistry , organic chemistry , electrode , mineralogy
A series of RE(Nc)(TBPP) ( 1−12 ) complexes [RE = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, Ho, Er, Tm; Nc = 2,3‐naphthalocyaninate; TBPP = meso ‐tetrakis(4‐ tert ‐butylphenyl)porphyrinate] and Eu[Nc( t Bu) 4 ](TClPP) [Nc( t Bu) 4 = tetra( tert ‐butyl)‐2,3‐naphthalocyaninate; TClPP = meso ‐tetrakis(4‐chlorophenyl)porphyrinate] ( 13 ) have been prepared by a one‐pot procedure which involves the treatment of RE(acac) 3 · n H 2 O (acac = acetylacetonate) with the corresponding metal‐free porphyrins and naphthalonitriles in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in n ‐octanol. These novel double‐deckers have been spectroscopically characterized. A one‐electron reduction and three one‐electron oxidations have been revealed by electrochemical methods. The potentials of all these processes depend linearly on the ionic radii of the central metal ions, giving a relatively large potential difference (0.50−0.57 V) between the first oxidation and the first reduction processes.