Coordination of a Potentially Tritopic Ligand via Phosphorus, Nitrogen and Oxygen: From Ligand Design to Heterobimetallic Metal–Organic Frameworks and Supramolecules,Crystal Growth & Design

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Coordination of a Potentially Tritopic Ligand via Phosphorus, Nitrogen and Oxygen: From Ligand Design to Heterobimetallic Metal–Organic Frameworks and Supramolecules
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2021-09-07 , DOI: 10.1021/acs.cgd.1c00701
Hans Gildenast ₁ , Franziska Busse ₂ , Ulli Englert _{1,

3}

Affiliation

The tritopic heterofunctional ligand 4-(3-(4-(diphenylphosphino)phenyl)-3-oxopropanoyl)benzonitrile (HL) combines a Pearson hard β-diketone, a soft nitrile, and an even softer phosphine group in one molecule. The hard cations Al^III and Fe^III selectively bind to the β-diketo site of the deprotonated ligand, but the resulting [ML₃] complexes could only be characterized by spectroscopic methods. The softer cations Hg^II and Pd^II selectively bind to the phosphine moiety rather than to the nitrile. Cross-linking of the [ML₃] metalloligands with soft cations affords both discrete aggregates and extended structures that could be structurally characterized. With Hg^II a neutral tetranuclear rectangle is obtained in which the O,O′ and the P donors act as coordination sites. Cross-linking with Ag^I involves both Pearson soft phosphane and nitrile groups and affords two porous metal–organic frameworks; in these 3D structures all three donor sites are employed. The reaction of [Cu(MeCN)₄]PF₆ with [AlL₃] leads to yet another degree of aggregation: namely, the octanuclear complex [(AlL₃)₄Cu₄](PF₆)₄. The crystal structure of this supramolecular cube features very large intra- and intermolecular voids.

中文翻译：

通过磷、氮和氧对潜在三元配体的协调：从配体设计到异双金属金属-有机框架和超分子

三元杂官能配体 4-(3-(4-(二苯基膦基)苯基)-3-氧代丙酰基)苄腈 (HL) 在一个分子中结合了 Pearson 硬 β-二酮、软腈和更软的膦基团。硬阳离子 Al ^III和 Fe ^III选择性地与去质子化配体的 β-二酮位点结合，但所得的 [ML ₃ ] 配合物只能通过光谱方法进行表征。较软的阳离子 Hg ^II和 Pd ^II选择性地与膦部分结合，而不是与腈结合。[ML ₃ ] 金属配体与软阳离子的交联提供了可以在结构上表征的离散聚集体和扩展结构。含汞^II获得中性四核矩形，其中 O、O' 和 P 供体充当配位点。与 Ag ^{I 的}交联涉及 Pearson 软磷烷和腈基团，并提供两种多孔金属 - 有机框架；在这些 3D 结构中，使用了所有三个供体位点。[Cu(MeCN) ₄ ]PF ₆与[AlL ₃ ]的反应导致另一种聚集程度：即八核络合物[(AlL ₃ ) ₄ Cu ₄ ](PF ₆ ) ₄。这种超分子立方体的晶体结构具有非常大的分子内和分子间空隙。

更新日期：2021-10-06

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