Photoconductivity in Metal–Organic Framework (MOF) Thin Films

Liu, Xiaojing; Kozłowska, Mariana; Okkali, Timur; Wagner, Danny; Higashino, Tomohiro; Brenner‐Weiß, Gerald; Marschner, Stefan; Fu, Zhaoming; Zhang, Qiang; Imahori, Hiroshi; Bräse, Stefan; Wenzel, Wolfgang; Wöll, Christof; Heinke, Lars

doi:10.1002/anie.201904475

Cited by 124 publications

(110 citation statements)

References 61 publications

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“…An interesting next step after the photoinduced occupation of a CT state is the complete dissociation of the corresponding exciton in a spatially separated electron and a hole. Next, we will discuss two examples: linker–linker and linker–guest interactions . In the first case, a naphthalenediimide linker‐based Co(II)‐MOF was studied .…”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

“…More recently, a host–guest porphyrinic MOF thin film showing pronounced photoconductivity was reported . Here, a donor–acceptor pair was formed by loading fullerenes (C 60 ) into the pores of the MOF.…”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

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: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

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Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…We speculate that the dimerization, which typically leads to the photobleaching of many spiropyran compounds, 17c is hindered by the anchoring at the MOF scaffold. Note, UV-induced photoconduction processes 25 or signicant electronic conduction due to spiropyran-to-merocyanine isomerization, 22 both increasing the conductivity, cannot be observed and have only a negligible inuence.…”

Section: Resultsmentioning

confidence: 99%

Proton-conduction photomodulation in spiropyran-functionalized MOFs with large on–off ratio

et al. 2020

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“…In addition, as a special subclass of MOFs, metal-porphyrin frameworks (also called porphyrinbased MOFs) have interesting properties for catalysis, conductivity and photo-electric effects. [37][38][39][40][41] Moreover, highly p-conjugated porphyrin based materials are well-known to exhibit good third-order NLO response, particularly the optical limiting effect. 42,43 Therefore, the porphyrin-based MOF thin lms may be promising materials for third-order NLO response, but no reports are available so far.…”

Section: Introductionmentioning

confidence: 99%