Introducing electrical conductivity to metal–organic framework thin films by templated polymerization of methyl propiolate

Sen, Beren; Santos, Jaciara C. C.; Haldar, Ritesh; Zhang, Qiang; Hashem, Tawheed; Qin, Peng; Liu, Ying; Kirschhöfer, Frank; Brenner‐Weiß, Gerald; Gliemann, Hartmut; Heinke, Lars; Barner‐Kowollik, Christopher; Knebel, Alexander; Wöll, Christof

doi:10.1039/d0nr06848a

Cited by 13 publications

(9 citation statements)

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“…The synthesis scheme follows general SURMOF principles but in a continuous manner and is able to work even without retention time. Using an Au-coated quartz crystal microbalance (QCM) sensor as a substrate does allow for direct mass-sensing, ,, and thus allows monitoring the growth in situ .…”

Section: Introductionmentioning

confidence: 99%

“…Regarding the controlled orientation and crystalline quality of the deposited MOF thin films, the layer-by-layer (LbL) deposition of surface-anchored MOFs (SURMOFs) has shown to yield excellent results. , However, LbL deposition requires careful optimization of reaction parameters, such as the choice of solvent, temperature, and time. As a result, SURMOF fabrication has been reported only for a limited number of MOF compounds, including MOF-2, HKUST-1, layer-pillared systems, ZIF-8, ZIF-67, and UiO-66 . On the other hand, exchanging linkers in those MOFs by following the principles of reticular synthesis and adding different functional moieties to these structures is relatively easily .…”

Section: Introductionmentioning

confidence: 99%

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Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

et al. 2023

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Fabrication of metal−organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus, far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal− organic frameworks (SURMOFs) has several requirements: mild conditions, low temperatures, day-long reaction times, and nonaggressive solvents. We herein present a fast method for the preparation of the MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50 and 2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. Scanning electron microscopy data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a poly(methyl methacrylate) layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as a Fabry−Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the ultraviolet−visible regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

et al. 2023

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“…15,16 However, LbL deposition requires careful optimization of reaction parameters, such as the choice of solvent, temperature, and time. As a result, SURMOF fabrication has been reported only for a limited number of MOF compounds, including MOF-2, HKUST-1, layer-pillared systems 17 , ZIF-8 18 , ZIF-67 19 , and UiO-66 20 . On the other hand, exchanging linkers in those MOFs by following the principles of reticular synthesis and adding different functional moieties to these structures is relatively easily.…”

Section: Introductionmentioning

confidence: 99%

“…The new synthesis scheme follows general SURMOF principles but in a continuous manner and is able to work even without retention time. Using an Au-coated quartz crystal microbalance (QCM) sensor as substrate does allow for direct mass-sensing 17,18,20 , and thus allows monitoring the growth insitu.…”

Section: Introductionmentioning

confidence: 99%

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

Monjezi

Okur

Limbach

et al. 2022

Preprint

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Fabrication of metal-organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal-organic frameworks (SURMOFs) has several requirements: Mild conditions, low temperatures, day-long reaction times, and non-aggressive solvents. We herein present a fast method for the preparation of the first MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50-2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in-situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. SEM data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a PMMA layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as Fabry-Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the UV-Vis regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds, led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

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“…Precipitation can significantly affect the reaction performance, for example, by leading to a non‐controlled and non‐uniform growth rate of MOF crystals in solution. Other methods that are particularly suitable for the generation of functional 2D porous crystalline molecular frameworks (e.g., 2D MOFs) are surface‐templated growth methods [ 5,6 ] or interfacial synthetic approaches (e.g., liquid/air or liquid/liquid interfaces). [ 7–9 ] Certainly, these methods can also suffer non‐controlled convective transport processes (e.g., surface‐tension‐driven convection (Marangoni convection)) and precipitation leading to fragmentation of the MOF films as well as to a poor control over their orientation, compactness, roughness profile, and/or morphology, features that greatly impact their function and performance.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 2D Porous Crystalline Materials in Simulated Microgravity

et al. 2021

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To date, crystallization studies conducted in space laboratories, which are prohibitively costly and unsuitable to most research laboratories, have shown the valuable effects of microgravity during crystal growth and morphogenesis. Herein, an easy and highly efficient method is shown to achieve space‐like experimentation conditions on Earth employing custom‐made microfluidic devices to fabricate 2D porous crystalline molecular frameworks. It is confirmed that experimentation under these simulated microgravity conditions has unprecedented effects on the orientation, compactness and crack‐free generation of 2D porous crystalline molecular frameworks as well as in their integration and crystal morphogenesis. It is believed that this work will provide a new “playground” to chemists, physicists, and materials scientists that desire to process unprecedented 2D functional materials and devices.

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Introducing electrical conductivity to metal–organic framework thin films by templated polymerization of methyl propiolate

Abstract: We herein present a case study on the templated, Pd-catalyzed polymerization reaction of methyl propiolate in the confined pore space of three different surface anchored metal-organic framework (SURMOFs) systems in...

Cited by 13 publications

References 59 publications

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

Synthesis of 2D Porous Crystalline Materials in Simulated Microgravity

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