A Chemiluminescent Metal–Organic Framework

Rühle, Bastian; Virmani, Erika; Engelke, Hanna; Hinterholzinger, Florian M.; Zons, Tobias von; Brosent, Birte; Bein, Thomas; Godt, Adelheid; Wuttke, Stefan

doi:10.1002/chem.201806041

Cited by 30 publications

(20 citation statements)

References 44 publications

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“…There are numerous other reports on luminescent MOFs assembled from chromophoric linkers based on, for example, biphenyl, naphthalene, anthracene, perylene, etc. (see review) …”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

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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“…There are numerous other reports on luminescent MOFs assembled from chromophoric linkers based on, for example, biphenyl, naphthalene, anthracene, perylene, etc. (see review) …”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…Furthermore, the solubility of the OBU may be compromised since increasing linker length is generally associated with decreasing solubility 143. Nevertheless, the possibilities to implement functionalities are huge: metallo‐OBUs with catalytic activity,144 fluorescence42c,145 or chemiluminescent OBUs,146 over biologic activity,21h,147 conductivity,148 all the way up to molecular rotors149 addressing the challenge to interlock dynamic functionality into a rigid backbone150 and multivariate functionality 69,151. Multiple functionalities can be aperiodically incorporated into the periodic organic backbone of reticular materials which opens the door to synergistic properties 152…”

Section: Inner Surface Functionalization and Multifunctional Efficiencymentioning

confidence: 99%

The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials

Ploetz

Engelke

Lächelt

et al. 2020

Adv Funct Materials

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231

145

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Nanoparticles have become a vital part of a vast number of established processes and products; they are used as catalysts, in cosmetics, and even by the pharmaceutical industry. Despite this, however, the reliable and reproducible production of functional nanoparticles for specific applications remains a great challenge. In this respect, reticular chemistry provides methods for connecting molecular building blocks to nanoparticles whose chemical composition, structure, porosity, and functionality can be controlled and tuned with atomic precision. Thus, reticular chemistry allows for the translation of the green chemistry principle of atom economy to functional nanomaterials, giving rise to the multifunctional efficiency concept. This principle encourages the design of highly active nanomaterials by maximizing the number of integrated functional units while minimizing the number of inactive components. State-ofthe-art research on reticular nanoparticles-metal-organic frameworks, zeolitic imidazolate frameworks, and covalent organic frameworks-is critically assessed and the beneficial features and particular challenges that set reticular chemistry apart from other nanoparticle material classes are highlighted. Reviewing the power of reticular chemistry, it is suggested that the unique possibility to efficiently and straightforwardly synthesize multifunctional nanoparticles should guide the synthesis of customized nanoparticles in the future.

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“…MOF materials may emit energy in the form of light upon excitation from a range of sources: incident light (photoluminescence), 115 heat (thermoluminescence), 116 electric current (electroluminescence), 117 chemical reactions (chemiluminescence), 118 mechanical stress (mechanoluminescence), 119 and ionizing radiation (radioluminescence) 120 are all examples of stimuli capable of producing a luminescence response. The luminescent signal may change in a variety of ways in the presence of target analytes: the emission intensity may be enhanced, 96,121 reduced (quenched), 122 or change in energy.…”

Section: Luminescent Sensor Readoutsmentioning

confidence: 99%