Metal–Organic Frameworks for the Exploitation of Distance between Active Sites in Efficient Photocatalysis

Gong, Xuan; Shu, Yufei; Jiang, Zhuo; Lu, Lingxiang; Xu, Xiaohui; Wang, Chao; Deng, Hexiang

doi:10.1002/anie.201915537

Cited by 122 publications

(94 citation statements)

References 57 publications

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“…Noteworthy, the activity of this reaction linearly correlates with the distance between the active centers. Therefore, a shorter distance between two porphyrin linkers resulted in an increased reactivity in the above mentioned reaction and thus highlights the potential of confinement and spatial arrangement in catalysis [23] …”

Section: Influence Of Topology and Alignment Of Active Sitesmentioning

confidence: 89%

Exploitation of Intrinsic Confinement Effects of MOFs in Catalysis

2021

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In catalysis research the design of bio‐inspired,'artificial enzymes‘ is a field of huge interest. These catalysts are distinguished by their high catalytic efficiency resulting from a close proximity of several active sites and secondary substrate‐catalyst interactions enabled by functional groups in the catalytic pocket. A class of materials which meets these requirements are metal‐organic frameworks (MOFs). Here, the pores confine a reaction environment where several functionalities can be incorporated and spatially positioned in a tunable fashion. Recently, a number of reports revealed the importance of such confinement effects for the control of catalytic activity and selectivity by exploiting the intrinsic properties like pore size and neighboring group effects and the alignment and distance of different active sites within one MOF pore. Thus, this concept aims to accentuate the potential of the exploitation of those effects in MOFs for the design of sophisticated catalysts.

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Section: Influence Of Topology and Alignment Of Active Sitesmentioning

confidence: 89%

Exploitation of Intrinsic Confinement Effects of MOFs in Catalysis

2021

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“…These MOFs are composed of Zr 6 O 8 clusters connected by different numbers of TCPP. The different topologies of the four MOFs result from the different kinds of coordination groups for Zr 4+ ion, leading to different pore sizes and distances of the inter TCPP active sites [11b] . MOF‐525 and PCN‐224 have similar pore size distribution (20 Å for MOF‐525 and 19 Å for PCN‐224) and similar distance between inter TCPP active sites (13.7 Å for MOF‐525 and 13.6 Å for PCN‐224) in the frameworks, which leads to almost the same absorption spectra (Figure 3b).…”

Section: Resultsmentioning

confidence: 99%

Effect of Topology on Photodynamic Sterilization of Porphyrinic Metal‐Organic Frameworks

Liu

Chen

Zhao

et al. 2021

Chemistry A European J

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Porphyrinic metal‐organic frameworks (MOFs) are promising photosensitizers due to the lack of self‐aggregation of porphyrin in aqueous solution. However, how the topology of porphyrinic MOFs affects the generation of singlet oxygen (1O2) is unclear. Here, the effect of the topology of porphyrinic MOFs on their photodynamic performance is reported. Four porphyrinic zirconium MOFs (MOF‐525, MOF‐545, PCN‐223 and PCN‐224 with different topologies: ftw, csq, shp and she, respectively) were selected to study the influence of topology on the photodynamic antibacterial performance. The 1O2 generation and the photodynamic antibacterial performance followed an decreasing order of MOF‐545>MOF‐525>PCN‐224>PCN‐223. The results reveal that the pore size, the distance between porphyrin, and the number of porphyrin per Zr6O8 cluster in MOFs greatly affected 1O2 generation. This work provides guidance for designing new MOFs for efficient photodynamic sterilization.

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“…Recently, highly defective MOF-525 structures with up to 50% linker vacancies were reported, further supporting the observation of high vacancy concentrations in our proposed structure of dPCN-224. 25,46 Both…”

Section: Resultsmentioning

confidence: 99%

“…56,57 Only recently, the notion that linker vacancies are prevalent also in the TCPP-based MOF-525 has gained attention, with vacancies reported up to 50%. 25,46 Here, we performed a comprehensive synthetic study on PCN-221 and undertook detailed investigations of the resulting structures using total scattering pair distribution function (PDF) analysis, powder and single crystal X-ray diffraction (PXRD/SCXRD), solid-state nuclear magnetic resonance (ssNMR) spectroscopy, and quantum-chemical calculations. We have determined that PCN-221 forms with orientationally disordered Zr6O4(OH)4 clusters, rather than Zr8O6 cubes, correlated with random vacant linker sites.…”

Section: Introductionmentioning

confidence: 99%

Disorder and Linker Deficiency in Porphyrinic Zr-MOFs: Resolving the Zr8O6 Cluster Conundrum in PCN-221

Koschnick¹,

Stäglich²,

Scholz³

et al. 2020

Preprint

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Porphyrin-based metal-organic frameworks (MOFs), exemplified by the prototypical representatives MOF-525, PCN-221, and PCN-224 are among the most promising MOF systems for catalysis, optoelectronics, and solar energy conversion. However, subtle differences between synthetic protocols for these three MOFs give rise to vast discrepancies in purported product outcomes and description of framework topologies. Here, we reveal the type and disorder of the Zr-clusters based on a comprehensive synthetic and structural analysis spanning local and long-range length scales. Our analysis on PCN-221 reveals Zr6O4(OH)4 clusters in four distinct orientations within the unit cell, rather than Zr8O6 clusters as originally published, accompanied by random linker vacancies around 50%. We propose disordered PCN-224 (dPCN-224) as a unified model to understand PCN-221, MOF-525, and PCN-224 by varying the degree of orientational cluster disorder, linker conformation and vacancies, and cluster—linker binding. Our work thus introduces a new perspective on network topology and disorder in Zr-MOFs and pinpoints the structural variables that direct their functional properties.

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Metal–Organic Frameworks for the Exploitation of Distance between Active Sites in Efficient Photocatalysis

Cited by 122 publications

References 57 publications

Exploitation of Intrinsic Confinement Effects of MOFs in Catalysis

Exploitation of Intrinsic Confinement Effects of MOFs in Catalysis

Effect of Topology on Photodynamic Sterilization of Porphyrinic Metal‐Organic Frameworks

Disorder and Linker Deficiency in Porphyrinic Zr-MOFs: Resolving the Zr8O6 Cluster Conundrum in PCN-221

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