Reversible structural switching of a metal–organic framework by photoirradiation

Nikolayenko, Varvara I.; Herbert, Simon; Barbour, Leonard J.

doi:10.1039/c7cc06074b

Cited by 45 publications

(44 citation statements)

References 37 publications

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“…For most DAE derivatives, the UV‐induced ring closing goes along with a slight change in the molecular length (by a few %) without further substantial changes in molecular components. Indeed, MOF materials containing DAE in their backbone showed slight changes in their structure, adsorption capacity, selectivity, and catalytic properties …”

Section: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 99%

“…In this respect, the remote control and photoswitching of the CO 2 adsorption capacity in MOF powders and pellets is envisioned to increase the efficiency and decrease the energy demand during the cycling of these processes. To this end, the switching of the CO 2 adsorption capacity of MOF powders with AB,98b,113,125,143,144,146 DAE, and SP moieties has been investigated.…”

Section: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 99%

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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: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 99%

Section: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…The significant difference in the CO 2 adsorption capacity is ascribed to the large motion of molecular fragments promoted by the photochemical reactions and the collapse of the cavity (Figure S31, Supporting Information). Such a route may provide significant alternatives for controlling expansion and contraction within a flexible framework by using light …”

Section: Resultsmentioning

confidence: 99%

“…Such ar oute may provide significant alternatives for controlling expansion and contraction within aflexible framework by using light. [24] To gain further insighti nto the surface-deformation response and relationship between macroscopic size shrinkage and microscopic-scale structuralt ransformations, atomicf orce microscopy (AFM) was used to revealf eatureso ft he Zn 2 -1 crystals. [25] As shown in Figure 6a Chem.E ur.J.…”

Section: Resultsmentioning

confidence: 99%

Photoinduced Nonlinear Contraction Behavior in Metal–Organic Frameworks

Shi

Chen

Zhang

et al. 2019

Chemistry A European J

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The photoinduced dynamic behavior of flexible materials has received considerable attention for potential applications, such as in data storage or as smart optical devices and molecular mechanical actuators. Until now, precisely controlling expansion and contraction with light has remained a challenge. Unraveling the detailed mechanisms of photoinduced structural transformations remains a critical step necessary to understand the molecular architecture necessary for the design of sensitive photomechanical actuators. Herein, a two‐dimensional flexible metal–organic framework [Zn2(bdc)2(3‐CH3‐spy)2]⋅H2O (Zn2‐1; H2bdc=1,4‐benzenedicaboxylic acid; 3‐CH3‐spy=3‐methylstyrylpyridine) with a positive volumetric thermal expansion coefficient of +78.78×10−6 K−1 is reported. Upon light irradiation at different wavelengths, the MOF underwent a [2+2] cycloaddition, which afforded a family of isomeric, three‐dimensional MOFs (Zn2‐2 n, n=a–d) in a single‐crystal‐to‐single‐crystal (SCSC) manner. An unprecedented phenomenon, that is, photoinduced nonlinear contraction (PINC), was observed during this conversion. The PINC is caused by conformational changes in the 3‐CH3‐spy and bdc2− ligands, the bending of metal–ligand bonds, and the local distortion of the paddle‐wheel SBUs. The formation of a “wrinkle morphology” on the crystal surface after the photoreaction was observed by AFM. This PINC behavior can broaden the studies on materials expansion and offer a photodriven approach for the future design of supersensitive photomechanical actuators.

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“…35,118,119 Pu, Guo and co-workers synthesized a five-fold interpenetrated MOF with biphenyldicarboxylate and DTE bispyridyl linkers (Figure 13a,b). 120 Despite of the large degree of the interpenetration, the resulting material had ca. 37% void volume in the unit cell, and readily responded to light with almost immediate colouration and decolouration of the crystals upon alternating irradiation with UV and visible light.…”

Section: Dithienylethenesmentioning

confidence: 99%