Inorganic Chemistry Frontiers
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2022
·Vol. 9
·期 17
·4506-4516
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IF 7.779
Dan Luo,Fei Wang,Chen-Hui Liu,San-Tai Wang,Ya-Yong Sun,Wei-Hui Fang,Jian Zhang
The sustainable development of nuclear energy urgently needs to focus on developing stable, efficient and low-cost adsorbent materials to tackle nuclear waste. We herein report a designed assembly of aluminum molecular rings (Al8) for effective iodine capture and aggregation. Instead of using expensive and rigid tetrapodand ligands, we succeeded in assembling Al8 with flexible pseudo-tetracarboxylic acid ligands (PT ligands, combining cheap and small ligands with transition metal centers) by the coordination-driven self-assembly strategy. Based on such an approach, we isolated a broad range of stable porous materials by regulating the PT ligands and achieved framework topology regulation (transformation from scu to ftw). Notably, this is the first time a porous assembly of Al8 with tetrapodand ligands is realized. The annular cavities in Al8 and a variety of pores created by PT ligands endow these materials with notable adsorption capacity towards iodine vapor molecules (73 wt% for AlOC-151 and 86 wt% for AlOC-155). As revealed by single-crystal X-ray diffraction studies, these annular cavities and pores act as reactors to induce the shape-matching formation of polyiodides with different aggregation states. Interestingly, the presence of Fe metal centers promotes the partial chemical reduction of iodine from I2 to Ix− (x = 3, 5), which is evidenced by the combination of bond valence sum (BVS) calculations, charge balancing, X-ray photoelectron spectroscopy (XPS) and conductivity measurements. This work has developed a synthetic approach for the preparation of porous frameworks and provides a reference for the designed synthesis of advanced radioactive capture adsorbent materials.
研究领域:
材料科学
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核能工程
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化学
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DOI
高影响因子
Aggregate
·
2022
·Vol. 4
·期 2
·e264
·
IF 0
San-Tai Wang,Ya-Jie Liu,Cheng-Cheng Feng,Wei-Hui Fang,Jian Zhang
It is of great interest to modulate the photophysical properties by atomically precise chemical control. The incorporation of conjugated ligands into crystalline materials provides a platform for molecular-level interpretation of the structure-activity relationship. Herein, we reported the phenol-thermal and scale-up synthesis of a new family of remarkably stable aluminum molecular rings. They are assembled by twenty Al III ions with large conjugated ligands and phenols, representing the currently largest sizes (up to 4 nm in diameter) in the field of main group metal oxo clusters. Phenols are not only reaction medium but also auxiliary bridging ligands on the surface of macrocyclic molecules. In addition, they are either parallel to the center of the molecular ring or inserted into the molecular ring, or form dimers/tetramers that bind macrocyclic molecules to form supramolecular structures. These macrocyclic rings are hydrophobic and ultra-stable, evidenced by retaining their morphology and crystalline when exposed to air for more than a year. Compared with the pristine conjugated ligands, they exhibit coordination-enhanced fluorescence. By dispersing them into a polydimethylsiloxane (PDMS) matrix, we prepared transparent and flexible PDMS thin films for coupling flexible display and nonlinear optical application. Our discovery of such atomically precise rings provides a platform for the fine-tuning of photo-related performances.
研究领域:
化学
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材料科学
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光学
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产品关联
DOI
CHINESE JOURNAL OF CHEMISTRY
·
2024
·
IF 5.5
Yi-Bo Chen,Cheng-Yang Zhang,Dan Luo,Ran-Qi Chen,Jian Zhang,Shu-Mei Chen,Wei-Hui Fang
Comprehensive Summary Macrocyclic compounds are of great interest for their ability to capture guest molecules into their cavities. In particular, host-guest interaction plays a crucial role in the formation of supramolecular compounds. Herein, two host-guest supramolecular compounds, [Al 8 (OH) 8 (L) 16 ]·2HL ( HL@AlOC-166 , HL = 4-Iodobenzoic acid) and [Al 8 (OH) 8 (L) 8 (L 1 ) 8 ]·2DMF ( DMF@AlOC-166 , HL 1 = isoamyl alcohol), are acquired by introducing different types of guest components based on the internal pore cavities of the aluminum molecular ring [Al 8 (OH) 8 (L) 16 ] ( AlOC-166 ). The inclusion of these guests is attributed to the presence of abundant hydrophilic OH serving as the hydrogen bond donors inward the ring cavity. Host-guest compounds usually exhibit superior nonlinear optical (NLO) response due to the existence of guest molecules that could change symmetry, dipole moments, charge distributions, etc . Unexpectedly, the AlOC-166 achieved the best NLO results, although it had no guest molecules inside its molecular ring, which breaks the traditional concept. The reason for this trend can be explained by the difference in intermolecular force rather than intramolecular interaction, mainly related to the amount and strength of π···π and C—I···π interactions in different compounds. This work investigates the effect of host-guest interaction on NLO, representing a new perspective for designing optical limiting materials.
研究领域:
化学
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材料科学
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产品关联
DOI
高影响因子
Science China-Chemistry
·
2023
·Vol. 66
·期 5
·1384-1393
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IF 9.6
Sun Yi-Fan,Liu Ya-Jie,Wang San-Tai,Liu Xiao-Yu,Ma Chao,Fang Wei-Hui,Zhang Jian
Based on our discovery of neutral aluminum molecular rings, we herein introduce rare earth ions into the center of the ring and reveal their structural adaptability. The resulting yoyo-like cationic macrocycles are highly adaptive to guests, creating unusual supramolecular assemblies. The first category is stacked with singly oriented rhombohedral channels, which exhibit fast and reversible solvent-triggered molecular motions and structural rearrangements The second type of assembly is that yoyo macrocycles and guest molecules form a nested host-guest sodalite cage supramolecular structure. It is uncommon for guest molecules to be well-defined within cages although caged structures have been well-documented Their host-guest interaction discussion reveals the self-adaptation and flexibility of the yoyo macrocycles. Considering their good water stability, we investigated their anion exchange properties. The results show that they have significant exchange capacity for KI/I 2 , \({\rm{Re}}{{\rm{O}}_4}^ - \) , and \({\rm{Mn}}{{\rm{O}}_4}^ - \) , revealing their potential application in water purification and nuclear waste treatment.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）