Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands
Arnold, Dennis, Biang, Yongzhong, Choi, Michael, Jiang, Jianzhuang, Li, Hung-Wing, Li, Renjie, Mak, Thomas C.W., Ng, Anthony, Ng, Dennis, Pan, Na, Sun, Xuan, Tao, Ye, Zhou, Zhong-Yuan, & Zhu, Peihua (2003) Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands. Journal American Chemical Society, 125(40), pp. 12257-12267.
A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic [(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.
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|Item Type:||Journal Article|
|Additional Information:||This article is freely available from the American Chemical Society website 12 months after the publication date. See links to publisher website in this record.|
|Subjects:||Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000)|
|Divisions:||Past > QUT Faculties & Divisions > Faculty of Science and Technology|
|Deposited On:||17 Jun 2009 13:56|
|Last Modified:||18 Jan 2016 04:24|
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