Synthesis, Characterization, and Properties of Half-Sandwich Iridium/Rhodium-Based Metallarectangles

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• 作者：Wen-Ying Zhang ; Ying-Feng Han ; Lin-Hong Weng ; Guo-Xin Jin
• 刊名：Organometallics
• 出版年：2014
• 出版时间：June 23, 2014
• 年：2014
• 卷：33
• 期：12
• 页码：3091-3095
• 全文大小：301K
• ISSN：1520-6041

文摘

Tetranuclear half-sandwich iridium or rhodium complexes were obtained in good yields from the reactions of the binuclear half-sandwich metal precursors [Cp*₂M₂(渭-CA)]Cl₂ (1a, M = Ir; 1b, M = Rh; CA = chloranilate) or [Cp*₂M₂(渭-DHNA)]Cl₂ (2a, M = Ir; 2b, M = Rh; H₂DHNA = 6,11-dihydroxynaphthacene-5,12-dione) with diPyNI (diPyNI = N,N-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) in the presence of AgOTf (OTf = CF₃SO₃) in CH₃OH, respectively. The new metallarectangles have been characterized by elemental analysis, FT-IR, ¹H NMR, electrospray mass spectrometry (ESI-MS), and UV/vis absorption spectroscopy. The interactions of these metallarectangles with aromatic molecules, especially pyrene, in solution have been studied by various NMR techniques (1D, DOSY, and ROESY) and UV鈥搗is absorption. DOSY measurements suggest that the interactions between metallarectangle 4a and pyrene are outside of the cavity. The strong 蟺路路路蟺 interactions between pyrene and the naphthalenetetracarboxydiimide ring of metallarectangle 4a were further supported by single-crystal X-ray diffraction data; pyrene molecules are found outside the cavity of the metallarectangle.