发光异质金属二膦-β-二克亚胺配合物中的协同作用

IF 6.4 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2023-12-22 DOI:10.1039/D3QI01740K

Frederic Krätschmer, Xiaofei Sun, David Frick, Christina Zovko, Wim Klopper and Peter W. Roesky

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引用次数: 0

摘要

双（膦）官能化β-二偏微配体[HC{(CH3)C}2{(o-[P(C6H5)2]2C6H4)N}2]-（PNac）被用于合成发光闭壳双金属配合物。结合了软和硬供体位点的 PNNP 口袋可以作为正交配体支架，选择性地配位两种不同的金属离子。通过与 [AuCl(tht)]（tht = 四氢噻吩）或 AgI 进行去质子化和随后的消盐反应，分别得到了单核配合物 [PNacAu] (1) 或 [PNacAg] (2)。AuI 离子与两个膦呈线性配位，形成一个 12 元金属大环，其中有一个空的β-二克亚胺口袋，可与硬 d10 金属离子（ZnII、CdII 和 HgII）络合。根据这一合成方案，分离出了一系列杂双金属配合物。第二种金属离子在空间上的近距离络合导致了光物理特性的急剧变化。为了进一步研究和理解，我们进行了量子化学计算。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Cooperativity in luminescent heterobimetallic diphosphine-β-diketiminate complexes†

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Cooperativity in luminescent heterobimetallic diphosphine-β-diketiminate complexes†

The bis(phosphine)-functionalized β-diketiminate ligand [HC{(CH₃)C}₂{(o-[P(C₆H₅)₂]₂C₆H₄)N}₂]⁻ (PNac) was used for the synthesis of luminescent closed-shell bimetallic complexes. The PNNP pocket combining both soft and hard donor sites can act as an orthogonal ligand scaffold to selectively coordinate two different metal ions. Deprotonation and subsequent salt elimination with [AuCl(tht)] (tht = tetrahydrothiophene) or AgI yielded the mononuclear complexes [PNacAu] (1) or [PNacAg] (2), respectively. The Au^I ion is linearly coordinated by the two phosphines, forming a 12-membered metalla-macrocycle with an empty β-diketiminate pocket available for complexation of hard d¹⁰ metal ions (Zn^II, Cd^II, and Hg^II). According to this synthetic protocol, a series of heterobimetallic complexes were isolated. The complexation of the second metal ion in close spatial proximity has led to drastic changes in the photophysical properties. For further studies and understanding, quantum chemical calculations were performed.