From supramolecular to solid state chemistry: crystal engineering of luminescent materials by trapping molecular clusters in an aluminium-based host matrix,Materials Horizons

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From supramolecular to solid state chemistry: crystal engineering of luminescent materials by trapping molecular clusters in an aluminium-based host matrix
Materials Horizons ( IF 12.2 ) Pub Date : 2020-06-23 , DOI: 10.1039/d0mh00637h
Clément Falaise _{1,

2,

3,

4,

5} , Anton A. Ivanov _{1,

2,

3,

4,

5} , Yann Molard _{6,

7,

8,

9,

10} , Maria Amela Cortes _{6,

7,

8,

9,

10} , Michael A. Shestopalov _{11,

12,

13,

14} , Mohamed Haouas _{1,

2,

3,

4,

5} , Emmanuel Cadot _{1,

2,

3,

4,

5} , Stéphane Cordier _{6,

7,

8,

9,

10}

Affiliation

Programming the supramolecular association of well-defined metal-based inorganic aggregates of different natures is an innovative concept to design materials. The emergence of such a strategy requires the mastering of (i) the handling of metallic aggregates in solution and (ii) the control of dynamic and subtle interactions (hydrogen bonding, electrostatic, van der Waals forces) at the nanoscopic scale. Herein, we report an appealing procedure, where γ-cyclodextrin (CD) is used as a host–guest stabilizing agent and structural linker, to organize luminescent molybdenum clusters [Mo₆Xⁱ₈Cl^a₆]²⁻ (X = Br and I) within well-ordered structures obtained from aqueous solutions. Such an approach enables the integration of the highly luminescent [Mo₆Iⁱ₈Cl^a₆]²⁻ clusters within the inert supramolecular architectures built-up from CD and aluminium oxo-hydroxo-aquo-clusters [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ (noted {Al₁₃}⁷⁺), which are optically silent in the absorption and emission spectral range. The charge is counter balanced by five Cl⁻ anions. Interactions between clusters, CD and Cl⁻ on one hand, and interactions between polycations and Cl⁻, on the other hand, lead to pseudo super-tetrahedrons {[Mo₆Iⁱ₈Cl^a₆]@2CD}Cl₄ and {Al₁₃}Cl₄, respectively, that share apices. This results in an open framework whose structure is related to that of lithium aluminosilicate LiAlSiO₄ (aka β-eucryptite). Compared to the usual cluster based compounds where the counter cations are alkalis or ammonium derivatives, in {Al₁₃}{[Mo₆Iⁱ₈Cl^a₆]@2CD}Cl₅·60H₂O, the number of clusters per unit cell volume dramatically decreases but their luminescence is not quenched. Indeed, the hybrid material shows excellent luminescent properties in the red-near infrared region with a quantum yield of 26%.

中文翻译：

从超分子化学到固态化学：通过将分子簇捕获在铝基基质中的发光材料的晶体工程

编程定义不同性质的金属基无机聚集体的超分子缔合是设计材料的创新概念。这种策略的出现要求掌握（i）在溶液中处理金属聚集体，以及（ii）在纳米尺度上控制动态和微妙的相互作用（氢键，静电，范德华力）。本文中，我们报道了一种有吸引力的程序，其中γ-环糊精（CD）被用作主体-客体稳定剂和结构连接剂，以组织发光的钼簇[Mo ₆ X ⁱ₈ Cl ^a₆ ] ^2-（X = Br和I）由水溶液获得的井井有条的结构中。这样的方法使得能够高度发光的集成[沫₆我^我₈氯^一个₆ ] ^2-内簇的惰性超分子结构建成从CD和铝氧代羟-水-簇[铝₁₃ ø ₄（OH）₂₄（H ₂ O）₁₂ ] ⁷⁺（表示为{Al ₁₃ } ⁷⁺），在吸收和发射光谱范围内是光学无声的。充电是反五个氯平衡^-阴离子。集群，CD和Cl之间的相互作用^-一方面，和聚阳离子和Cl之间的相互作用^-，在另一方面，导致伪超四面体{[沫₆我^我₈氯^一个₆ ] @ 2CD}氯₄和{的Al₁₃ }氯₄，分别共享顶点。这导致其结构与铝硅酸锂LiAlSiO₄（akaβ-锂霞石）的结构有关的开放框架。与抗衡阳离子为碱或铵衍生物的常见簇基化合物相比，{Al₁₃ } {[Mo₆ Iⁱ₈ Cl^a₆ ] @ 2CD} Cl₅·60H ₂ O，每单位细胞体积的簇数显着减少，但其发光没有被淬灭。实际上，该杂化材料在红-近红外区域显示出优异的发光性能，量子产率为26％。

更新日期：2020-09-01

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