On-Surface Synthesis of Highly Oriented Thin Metal–Organic Framework Films through Vapor-Assisted Conversion

Virmani, Erika; Rotter, Julian M.; Mähringer, Andre; Zons, Tobias von; Godt, Adelheid; Bein, Thomas; Wuttke, Stefan; Medina, Dana D.

doi:10.1021/jacs.7b08174

Cited by 153 publications

(187 citation statements)

References 39 publications

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“…SURMOFs are also well suited as model systems for more conventional applications, e.g., for uptake and diffusion studies . Thin MOF films can be prepared using various methods, such as vapor‐assisted growth and chemical vapor deposition (Figure a,b). The huge interest in MOF thin films has resulted in the development of a variety of additional coating schemes, including various one‐pot synthesis and sol‐gel methods, as well as inkjet printing, employing polymer composites and spin‐coating of MOF nanoparticles.…”

Section: Mofs Mof Thin Films and Surface‐anchored Mofs (Surmofs)mentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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In recent years, a particularly attractive and novel strategy has become available for the fabrication of photoresponsive, porous, and crystalline molecular solids from appropriately functionalized chromophoric linkers. The crystallinity of these materials allows a rather straightforward description and analysis using theoretical methods, thus tremendously accelerating the design of novel materials. This new class of crystalline molecular solids is referred to as metal-organic frameworks, MOFs (or porous coordination polymers, PCPs). [1] MOFs are constructed from metal-/metal-oxo nodes and organic linkers (Figure 1). The incorporation of photoactive species into MOFs may be realized by using them as linkers (method L) or attaching them to a linker (method A), as shown in Figure 1a. In addition, the porosity of MOFs allows the loading of chromophoric compounds as guests (method G) into the pores of this interesting framework material.In this review article, we mainly focus on organic photoactive species, which are either simply loaded as guests into porous MOFs or used after appropriate functionalization as building blocks for the construction of the framework (methods L, A, and G). [2] It is important to note that in the context of photoresponsive behavior, MOFs carry a potential which by far exceeds that of nonporous coordination polymers. This is because simple loading of guest/solvent molecules of different size/polarity/functionality in the MOF pores can impart a large optical response, which is useful, e.g., for sensing applications. [3] As an example, the solvent-dependent optical response or solvatochromism [4] is illustrated in Figure 1b. Such effects cannot be realized for nonporous coordination polymers.The different types of photoresponsive molecules addressed in this review can be grouped into two classes. The first contains molecules where the structure remains essentially unchanged upon light-induced electronic excitation, and the second contains molecular species that change their structure or conformation upon absorption of photons (molecular switches).Light with a wavelength in the range 200-800 nm (6.2-1.5 eV) can excite a molecule to a transient excited electronic state. The transient state then decays to a low-energy state, either the parent ground state or another longer-lived excited state. Decay time scales are in the range 10 −12 -10 1 s, and the released energy can be radiative or nonradiative in nature. For many applications, nonradiative energy loss is unwanted, When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well-defined structure carry substantial advantages over amorphous materials. Here, the metal-organic framework (MOF)-based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coo...

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Section: Mofs Mof Thin Films and Surface‐anchored Mofs (Surmofs)mentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…Film growth was achievedb yv apor-assisted conversion ( Figure S2), whichh as recently been developed for the synthesis of thin films of UiOs. [19] In the present case, ad ropleto fD MF containing PAP diacid, ZrOCl 2 ,a nd acetic acid was drop-cast onto the substrate, which had been placeds lightly above the level of amixture of DMF and acetic acid, and then the glass container was sealed. After 24 ha t1 00 8C, af ilm with ap referential orientation of the crystals along the 111 axis was obtained (peak at 4.78 2q in Figure 1b), as evidenced by XRD measurements ( Figure 1b andF igure S4) and 2D grazing incidence wide angle Xray scattering (GIWAXS) (Figure 1d)m easurements.…”

Section: Resultsmentioning

confidence: 99%

“…The films were prepared on glass slides that had been modified with a self‐assembled monolayer providing a carboxylic acid functionalized surface (Figure S1). Film growth was achieved by vapor‐assisted conversion (Figure S2), which has recently been developed for the synthesis of thin films of UiOs . In the present case, a droplet of DMF containing PAP diacid, ZrOCl 2 , and acetic acid was drop‐cast onto the substrate, which had been placed slightly above the level of a mixture of DMF and acetic acid, and then the glass container was sealed.…”

Section: Resultsmentioning

confidence: 99%

A Chemiluminescent Metal–Organic Framework

Rühle

Virmani

Engelke

et al. 2019

Chemistry A European J

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The synthesis and characterization of a chemiluminescent metal–organic framework with high porosity is reported. It consists of Zr6O6(OH)4 nodes connected by 4,4′‐(anthracene‐9,10‐diyl)dibenzoate as the linker and luminophore. It shows the topology known for UiO‐66 and is therefore denoted PAP‐UiO. The MOF was not only obtained as bulk material but also as a thin film. Exposure of PAP‐UiO as bulk or film to a mixture of bis‐(2,4,6‐trichlorophenyl) oxalate, hydrogen peroxide, and sodium salicylate in a mixture of dimethyl and dibutyl phthalate evoked strong and long lasting chemiluminescence of the PAP‐UiO crystals. Time dependent fluorescence spectroscopy on bulk PAP‐UiO and, for comparison, on dimethyl 4,4′‐(anthracene‐9,10‐diyl)dibenzoate provided evidence that the chemiluminescence originates from luminophores being part of the PAP‐UiO, including the luminophores inside the crystals.

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“…We hypothesized that moisture in the ambient air aids VPLE, compared to dry argon and nitrogen. [25] The catalyzing effect of moisture was confirmed by adding water vapor after evacuating the reaction vessel, to achieve 5% relative humidity at 298 K. VPLE under these conditions led to the incorporation of 63 %C HO-Im after 24 h. Since neither ZIF-8 nor ZIF-90 have significant water uptakes at such al ow relative humidity (Figure S23), the effect is likely due to co-adsorption of water with the incoming linker. We hypothesize that, similar as for acid gases in ZIFs,t he incoming linker and water form am ore reactive complex.…”

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confidence: 95%