Designing Cage-Supported Cluster-Organic Framework for Highly Efficient Optical Limiting

Abstract

Making metal−organic cages into a cluster-organic framework is rarely known and may bring interesting functions. Ti 4 L 6 (where L = embonate) is an ultrastable tetrahedron that can be used as a 4-connecting crystal engineering tecton. In this work, we first obtain two unique Ti 4 L 6 cagesupported cluster-organic frameworks including the globular [Ba 6 (μ 2 −OH) 8 ] 4+ cluster and the hollow α-Keggin-type [Zn 12 (μ 3 −OH) 4 (μ 2 −OH) 12 ] 8+ cluster, respectively. Such extraordinary assembly significantly enhances their structural stability, so that both of them have notable optical limiting performances.

Combination of dimensional reduction and active site addition strategies for preparing unique {RE9}-cluster-based MOFs: efficient CO2 fixation and Knoevenagel condensation

“…Metal-organic frameworks (MOFs) containing different polynuclear metal-oxo clusters are unique porous crystalline materials with widespread promise for sensing, heterogeneous catalysis and gas storage/separation. [15][16][17][18][19][20][21] Recent studies have exhibited that polynuclear cluster-based rare-earth (RE) MOFs possess exceedingly high stability and abundant catalytic active sites, [22][23][24] in which the catalytic efficiency for CO 2 con-version and Knoevenagel condensation could be greatly accelerated by the synergistic effect of activated metal ions (Lewis acid sites, LASs) and nucleophilic groups (Lewis base sites, LBSs). 25,26 However, the accessibility of these RE-MOF materials to sterically demanding substrates is limited by expanding and stabilizing the active sites.…”

Integrated Anionic Zirconium‐Organic Cage and Cationic Boron‐Imidazolate Cage for Synergetic Optical Limiting

“…[22][23][24] The molecular nature of these charged coordination cages endows them with easy solution-processability unattainable with traditional framework materials. Specifically speaking, by using such soluble and stable (Ti 4 L 6 ) 8À or (Zr 4 L 6 ) 8À cage as a precursor to assembly with various metal ions and organic ligands, we have obtained a variety of advanced cage-based architectures, including a series of co-crystals (PTC-235 [25] and PTC-296 [26] ), surfacemodified cages (PTC-371 [27] ) and 3D frameworks (PTC-236 [28] and PTC-320 [29] ). The potential application prospects of these assembled materials in molecular recognition/ separation, storage/encapsulation and optics have been well demonstrated.…”