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Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands
Bian, YZ; Jiang, JZ; Tao Y(陶冶); Tao, Y; Choi, MTM; Li, RJ; Ng, ACH; Zhu, PH; Pan, N; Sun, X; Arnold, DP; Zhou, ZY; Li, HW; Mak, TCW; Ng, DKP
2003
发表期刊JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷号125期号:40页码:12257-12267
通讯作者Shandong Univ, Dept Chem, Jinan 250100, Peoples R China ; Chinese Acad Sci, Lab Synchrotron Radiat, Inst High Energy Phys, Beijing 100039, Peoples R China ; Chinese Univ Hong Kong, Dept Chem, Shatin, Hong Kong, Peoples R China ; Queensland Univ Technol, Sch Phys & Chem Sci, Synthesis & Mol Recognit Program, Brisbane, Qld 4001, Australia
摘要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 L(III)-edge X-ray absorption near-edge structure (XANES) profiles.
文章类型Article
学科领域Chemistry
研究领域[WOS]Chemistry
DOI10.1021/ja036017+
URL查看原文
语种英语
WOS类目Chemistry, Multidisciplinary
WOS记录号WOS:000185784700042
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被引频次:129[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.ihep.ac.cn/handle/311005/240186
专题多学科研究中心
作者单位中国科学院高能物理研究所
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Bian, YZ,Jiang, JZ,Tao Y,et al. Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2003,125(40):12257-12267.
APA Bian, YZ.,Jiang, JZ.,陶冶.,Tao, Y.,Choi, MTM.,...&Ng, DKP.(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 OF THE AMERICAN CHEMICAL SOCIETY,125(40),12257-12267.
MLA Bian, YZ,et al."Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 125.40(2003):12257-12267.
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