Photochromic 2D Metal-Organic Framework Nanosheets (MONs): Design, Synthesis, and Functional MON-Ormosil Composite

Mukhopadhyay, Arindam; Maka, Vijay Kumar; Savitha, G.; Moorthy, Jarugu Narasimha

doi:10.1016/j.chempr.2018.03.013

Cited by 78 publications

(61 citation statements)

References 75 publications

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“…Therefore, modulation of spectrokinetic properties of the photogenerated colored species continues to be a subject of fundamental interest in research on photochromic diarylpyrans. [15][16][17][18][19][20] One of the major research interests in our own laboratories has been focused, for quite some time, on modulation of the photochromic properties of diarylpyrans by rational molecular design approach and development of photoresponsive organic [21][22][23][24][25][26][27][28] and metalorganic materials 29 by exploiting diarylpyran as the design element. Over the past decade, we have comprehensively established the profound influence of aromatic annulation, 21 electronic effects transmitted by arylation 22,23 /arylethynylation, 24 toroidal conjugations extant to the systems based on hexaphenylbenzenes, 25 through-space electronic effects in cofacially oriented arenes, 26 helicity as a steric force, 27 etc., on the stabilization of the otherwise fleeting o-quinonoid colored intermediates photogenerated from diarylbenzopyrans.…”

Section: Introductionmentioning

confidence: 99%

Influence of silyloxy substitution on the photochromic properties of diarylbenzo- and naphthopyrans $$^{\S }$$ §

2018

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Diarylbenzopyrans and their annulated derivatives are a class of photochromic compounds, which have been extensively investigated for photochromism. In fact, some naphthopyrans are employed industrially in ophthalmic lens applications. Photoirradiation of 2,2-diphenylbenzopyran leads to the formation of colored o-quinonoid intermediates. The latter revert too rapidly to allow their observation only at low temperatures (173-263 K). Annulation and other strategies are exploited to observe the colored o-quinonoid intermediates that persist for a few minutes at room temperature. We have examined photochromism of a set of silyloxysubstituted 2,2-diphenylbenzo-and naphthopyrans to explore how the mesomeric effects transmitted by the strongly e-donating silyloxy group substituted in the ring and at phenyl groups manifest in the spectrokinetic properties of their photogenerated colored o-quinonoid intermediates. We show that silyloxy substitution in the benzopyran ring leads to remarkable stabilization of the colored intermediates to enable their persistence at 283 K for a few minutes. In contrast, similar substitution in the C2-phenyl rings destabilizes the colored intermediates.

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Section: Introductionmentioning

confidence: 99%

Influence of silyloxy substitution on the photochromic properties of diarylbenzo- and naphthopyrans $$^{\S }$$ §

2018

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“…Up to now, the methods for synthesizing 2D MOFs can be classified into two groups: top-down and bottomup strategies. The top-down exfoliation approach relies on the disintegration of 3D layered MOF solid 11,[16][17][18][19] , usually suffering from high-energy consumption, fragmentation and morphological damage and low yields (typically < 15%) 9,20 . For the bottomup strategy, 2D MOFs are synthesized directly from starting materials by solvothermal route using additives (e.g., surfactant, capping molecules, template) to control the oriented MOF growth [21][22][23][24][25] .…”

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confidence: 99%

CO2 controls the oriented growth of metal-organic framework with highly accessible active sites

Zhang

et al. 2020

Nat Commun

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The production of 2D metal-organic frameworks (MOFs) with highly exposed active surfaces is of great importance for catalysis. Here we demonstrate the formation of MOF nanosheets by utilizing CO 2 as a capping agent to control the oriented growth of MOF. This strategy has many advantages over the conventional methods. For example, it is template-free and proceeds at mild temperature (35°C), CO 2 can be easily removed by depressurization, and the properties of the MOF nanosheets can be well adjusted by changing CO 2 pressure. Such a simple, rapid, efficient and adjustable route produces MOF nanosheets with ultrathin thickness (∼10 nm), small lateral size (∼100 nm) and abundant unsaturated coordination metal sites on surfaces. Owing to these unique features, the as-synthesized MOF nanosheets exhibit superior activity for catalyzing the oxidation reactions of alcohols.

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“…4). Hence, a variety of MOF and COF nanosheets can be synthesized by top-down methods such as sonication exfoliation [37][38][39], mechanical exfoliation [40,41], and chemical exfoliation [42,43]. It is relatively simple and efficient to prepare MOF and COF nanosheets from layered bulk materials by top-down methods.…”

Section: Top-down Methodsmentioning

confidence: 99%

Emerging porous nanosheets: From fundamental synthesis to promising applications

et al. 2020

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Metal-organic framework (MOF) nanosheets and covalent organic framework (COF) nanosheets as emerging porous materials nanosheets have captured increasing attention owing to their attractive properties originating from the advantages of large lateral size, ultrathin thickness, tailorable physiochemical environment, flexibility and highly accessible active sites on surface, and the applications of them have been explored in a wide range of fields. Although MOF and COF nanosheets own many similar properties, their applications in various fields show significant differences, probably due to their different compositions and bonding modes. Hence, we summarize the recent progress of MOF and COF nanosheets by comparative analysis on their advantages and limitations in synthesis and applications, providing a more profound and full-scale perspective for researchers or beginners to understand this field. Herein, the categories of preparation methods of MOF and COF nanosheets are firstly discussed, including top-down and bottom-up methods. Secondly, the applications of MOF and COF nanosheets for separation, catalysis, sensing and energy storage are summarized. Finally, based on current achievements, we put forward our personal insights into the challenges and outlooks on the synthesis, characterizations, and promising applications for future research of MOF and COF nanosheets. KEYWORDS metal-organic framework (MOF) nanosheets, covalent organic framework (COF) nanosheets, top-down methods, bottom-up methods, two-dimensional (2D) nanomaterials

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Photochromic 2D Metal-Organic Framework Nanosheets (MONs): Design, Synthesis, and Functional MON-Ormosil Composite

Cited by 78 publications

References 75 publications

Influence of silyloxy substitution on the photochromic properties of diarylbenzo- and naphthopyrans $$^{\S }$$ §

Influence of silyloxy substitution on the photochromic properties of diarylbenzo- and naphthopyrans $$^{\S }$$ §

CO2 controls the oriented growth of metal-organic framework with highly accessible active sites

Emerging porous nanosheets: From fundamental synthesis to promising applications

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