Phosphonate Lanthanide Carbonate Cages: Remarkably Aggregated Lanthanide-Oxo Cores with Removable Cation Templates

IF 3.4 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Crystal Growth & Design Pub Date : 2025-02-24 DOI:10.1021/acs.cgd.5c00082

Chaolun Wei, Xiaojuan Li, Yi Liu, Hai-Ye Li*, Houting Liu* and Haiquan Tian*,

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Abstract

Phosphonate lanthanide carbonate cages represent a fascinating class of clusters capable of supplying carbonate ions to the center of the cages; furthermore, the phosphonate ligands enclose the exterior. By removing sodium templating cations and regulating the release of carbonate templating anions, two significantly aggregated lanthanide shell–core–shell topologies have now been synthesized through the reaction of lanthanide naphthalene-functionalized phosphonates and two differently terminated C₂-symmetric double hydrazones. The resulting two new phosphonate dysprosium carbonate cages [Dy₁₂Na₂₆(μ₃-O₃PC₁₁H₉)(μ₄-O₃PC₁₁H₉)(μ₆-O₃PC₁₁H₉)₉(μ₈-CO₃)₇(μ₉-CO₃)₃(L¹)₅(μ₃-O)₆(μ₂-O)₁₀(DMF)₆(H₂O)₉]·5DMF·4MeCN·4H₂O (1) and [Dy₂₂(μ₃-O₃PC₁₀H₇)₄(μ₅-O₃PC₁₀H₇)₄(μ₆-O₃PC₁₀H₇)₆(μ₅-CO₃)₂(μ₆-CO₃)₄(L²)₄(μ₂-COO)₄(μ₃-O)₄(μ₂-O)₂(H₂O)₁₁]·95MeOH·78H₂O (2) were obtained. Two types of hydrazones function as tridecadentate and enneadentate intercepted coligands, coordinating the periphery of phosphonate dysprosium carbonate cages. The mixed hexacosaple sodium and decaple carbonate ions act as templating cations and anions for constructing heterobimetallic 1 by filling the void, showcasing the ability to effectively control dysprosium cage aggregation in homometallic 2 through the removal of the cation and anion templates. Additionally, it was noted that the aggregation of the dysprosium shell–core–shell cages significantly influences the magnetic relaxation behavior, shifting from a field-induced two-step process in 1 to a zero-field one-step process in 2.

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磷酸盐镧系碳酸盐笼：显着聚集镧系氧化物芯与可移动阳离子模板

磷酸盐镧系碳酸盐笼代表了一类迷人的簇，能够向笼的中心提供碳酸盐离子；此外，磷酸盐配体包裹了外部。通过去除钠模板阳离子和调节碳酸盐模板阴离子的释放，通过镧系萘功能化膦酸盐和两个不同端部的c2对称双腙的反应，合成了两个显著聚集的镧系壳核壳结构。得到了两种新型磷酸盐型碳酸镝笼[Dy12Na26(μ3-O3PC11H9)(μ4-O3PC11H9)(μ6-O3PC11H9)9(μ8-CO3)7(μ9-CO3)3(L1)5(μ3-O)6(μ2-O)10(DMF)6(H2O)9]·5DMF·4MeCN·4H2O(1)]和[Dy22(μ3-O3PC10H7)4(μ6-O3PC10H7) 4(μ6-O3PC10H7)6(μ5-CO3)2(μ6-CO3)4(L2)4(μ2-COO)4(μ3-O)4(μ2-O)2(μ2-O)2(H2O)11]·95MeOH·78H2O(2)]。两种类型的腙作为三齿形和十齿形拦截共配体，协调磷酸盐型碳酸镝笼的外围。混合的六聚钠和十聚碳酸钠离子作为模板阳离子和阴离子，通过填充空隙来构建杂双金属1，显示了通过去除阳离子和阴离子模板来有效控制同金属2中镝笼聚集的能力。此外，还注意到镝壳-核-壳笼的聚集显著影响磁弛豫行为，从1中的场诱导两步过程转变为2中的零场一步过程。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.