Post‐Assembly Modification of Homochiral Titanium–Organic Cages for Recognition and Separation of Molecular Isomers

Chen, Guanghui; He, Yan‐Ping; Yang, Yu; Lv, Hong; Li, Shangda; Wang, Fei; Gu, Zhengbiao; Zhang, Jian

doi:10.1002/anie.202300726

Cited by 15 publications

(9 citation statements)

References 77 publications

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“…In order to visually observe the internal morphology of one-dimensional pores, we used Mercury 46 to simulate their pore structure using the contact surface method (Figures S39−S42). 47 Notably, [AlOC-199-L]•O n Pr can be scaled up for synthesis at the gram level (a single experiment can obtain 2.1 g of sample), which provides a foundation for subsequent performance exploration and practical application research (Figure 3a). The air stability, solvent stability, and thermal stability are confirmed by powder X-ray diffraction (PXRD) patterns of their bulk samples (Figures 3b and S43−S45).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Considering the chiral structural features and the existence of considerable pore channels, we attempted to use it for enantiomeric separation of racemic 1-phenethylalcohol (PEOH) and obtained enantiomeric excess resolutions of 10.1% for the S-configurations of PEOH, this also validates homochiral channels from another perspective (Figures S48 and S49). 47 Given the one-dimensional channels and the presence of counter-anions in its structure, we performed anion-exchange experiments. The result showed that it not only exchanges inorganic anions like MnO 4 − (Figure S50), but also adsorbs large organic dye molecules.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Assembly of Homochiral Aluminum Oxo Clusters for Circularly Polarized Luminescence

Chen,

Wang,

Liu

et al. 2024

J. Am. Chem. Soc.

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Chiral aluminum oxo clusters (cAlOCs) are distinguished from other classes of materials on account of their abundance in the earth's crust and their potential for sustainable development. However, the practical synthesis of cAlOCs is rarely known. Herein, we adopt a synergistic coordination strategy by using chiral amino acid ligands as bridges and auxiliary pyridine-2,6dicarboxylic acid as chelating ligands and successfully isolate an extensive family of cAlOCs. They integrate molecular chirality, absolute helicity, and intrinsic hydrogen-bonded chiral topology. Moreover, they have the structural characteristics of onedimensional channels and replaceable counteranions, which make them well combined with fluorescent dyes for circularly polarized luminescence (CPL). The absolute luminescence dissymmetry factor (g lum ) of up to the 10 −3 order is comparable to several noble metals, revealing the enormous potential of cAlOCs in low-cost chiral materials. We hope this work will inspire new discoveries in the field of chirality and provide new opportunities for constructing low-cost chiral materials.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Assembly of Homochiral Aluminum Oxo Clusters for Circularly Polarized Luminescence

Chen,

Wang,

Liu

et al. 2024

J. Am. Chem. Soc.

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“…A large number of researchers meet the requirements of organic catalysis by designing the SBUs and organic ligands of MOFs. 17−19 In recent years, titanium oxide clusters, 20 zirconium oxygen clusters, 21 polyoxometalates, 22 transition-metal oxygen clusters, 23,24 and rare-earth oxygen clusters 25 have been successively discovered. These clusters can be applied for various organic catalysis because they not only have multiple catalytic centers but also can effectively enrich substrates as nanoreactors 26−28 to improve the catalytic performance through the confinement effect.…”

Section: ■ Introductionmentioning

confidence: 99%

Highly Stable 72-Nuclearity Nanocages for Efficient Synthesis of Aryl Nitriles via Ni/Cu Synergistic Catalysis

Liang,

Zhang,

Jiao

et al. 2024

J. Am. Chem. Soc.

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Seeking noble-metal-free catalysts for efficient synthesis of aryl nitriles under mild conditions poses a significant challenge due to the use of hypertoxic cyanides or high-pressure/ temperature NH 3 /O 2 in conventional synthesis processes. Herein, we developed a novel framework 1 assembled by [Ni 72 ] nanocages with excellent solvents/pH stability. To investigate the structure− activity relationship of catalytic performance, several isostructural MOFs with different molar ratios of Ni/Cu by doping Cu 2+ into framework 1 (Ni 0.59 Cu 0.41 (2), Ni 0.81 Cu 0.19 (3), Ni 0.88 Cu 0.12 (4), and Ni 0.92 Cu 0.08 ( 5)) were prepared. Catalytic studies revealed that catalyst 3 exhibited remarkable performance in the synthesis of aryl nitriles, utilizing a formamide alternative to hypertoxic NaCN/KCN. Notably, catalyst 3 achieved an excellent TOF value of 9.8 h −1 . Furthermore, catalyst 3 demonstrated its applicability in a gram-scale experiment and maintained its catalytic performance even after six recycling cycles, owing to its high stability resulting from significant electrostatic and orbital interactions between the Ni center and ligands as well as a large SOMO−LUMO energy gap supported by DFT calculations. Control experiments and DFT calculations further revealed that the excellent catalytic performance of catalyst 3 originated from the synergistic effect of Ni/Cu. Importantly, this work not only provides a highly feasible method to construct highly stable MOFs containing multinuclear nanocages with exceptional catalytic performance but also represents the first example of a heterogeneous catalyst for the synthesis of aryl nitriles using formamide as the cyanide source.

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“…These characteristics facilitate the study of the PTC-236 in host-guest chemistry via single-crystal-to-single-crystal (SC-SC) transformation. Gratifyingly, PTC-236 was successfully utilized for the X-ray diffraction analyses of more than 20 guests, [11] including benzene (PhH) and its derivatives, aromatic/aliphatic nitriles, and aromatic alcohol molecules. Indeed, the hostguest interactions between the titanium cage and captured guests can be observed clearly.…”

Section: Introductionmentioning

confidence: 99%

Post‐Assembly Modification of Homochiral Titanium–Organic Cages for Recognition and Separation of Molecular Isomers

Chen

Yang

et al. 2023

Angewandte Chemie

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A chiral metal-organic cage (MOC) was extended and fixed into a porous framework using a post-assembly modification strategy, which made it easier to study the host-guest chemistry of the solidstate MOC using a single-crystal diffraction technique. Anionic Ti 4 L 6 (L = embonate) cage can be used as a 4connecting crystal engineering tecton, and its optical resolution was achieved, thus homochiral ΔΔΔΔ-and ΛΛΛΛ-[Ti 4 L 6 ] cages were obtained. Accordingly, a pair of homochiral cage-based microporous frameworks (PTC-236(Δ) and PTC-236(Λ)) were easily prepared by a post-assembly reaction. PTC-236 has rich recognition sites provided by the Ti 4 L 6 moieties, chiral channels and high framework stability, affording a single-crystal-tosingle-crystal transformation for guest structure analyses. Thus it was successfully utilized for the recognition and separation of isomeric molecules. This study provides a new approach for the orderly combination of well-defined MOCs into functional porous frameworks.

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Post‐Assembly Modification of Homochiral Titanium–Organic Cages for Recognition and Separation of Molecular Isomers

Cited by 15 publications

References 77 publications

Assembly of Homochiral Aluminum Oxo Clusters for Circularly Polarized Luminescence

Assembly of Homochiral Aluminum Oxo Clusters for Circularly Polarized Luminescence

Highly Stable 72-Nuclearity Nanocages for Efficient Synthesis of Aryl Nitriles via Ni/Cu Synergistic Catalysis

Post‐Assembly Modification of Homochiral Titanium–Organic Cages for Recognition and Separation of Molecular Isomers

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