Diverse Multi‐Functionalized Oligoarenes and Heteroarenes for Porous Crystalline Materials

Grosjean, Sylvain; Hassan, Zahid; Wöll, Christof; Bräse, Stefan

doi:10.1002/ejoc.201801232

Cited by 20 publications

(17 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…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) . 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.…”

Section: Introductionmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

Self Cite

View full text Add to dashboard Cite

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...

show abstract

Section: Introductionmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Um den Einfluss unterschiedlicher Alkylsubstituenten auf die subtile Balance zwischen Lçslichkeit und Niederschlag weiter zu untersuchen, synthetisierten wir BDBA-Me [38] und BDBA-Et mit Me-oder Et-Gruppen in 2,5-Position (blau in Abbildung 1a). Wiee rwartet bildeten sich nach fünf Tagen die neuen kubischen Käfige 1-Me und 1-Et aus THF-Lçsungen von TBTQ-n Bu und BDBA-X (X = Me oder Et) im Verhältnis 2:3n ach wiederholter Zugabe von 4--Molekularsieb (siehe Hintergrundinformationen füre xperimentelle und analytische Details).…”

Section: Ergebnisse Und Diskussionunclassified

Isoretikuläre Kristallisation von hochporösen kubischen kovalentorganischen Käfigverbindungen**

et al. 2021

View full text Add to dashboard Cite

Modular frameworks featuring well-defined pore structures in microscale domains establish tailor-made porous materials. For open molecular solids however, maintaining long-range order after desolvation is inherently challenging, since packing is usually governed by only a few supramolecular interactions. Here we report on two series of nanocubes obtained by co-condensation of two different hexahydroxy tribenzotriquinacenes (TBTQs) and benzene-1,4-diboronic acids (BDBAs) with varying linear alkyl chains in 2,5-position.n Butyl groups at the apical position of the TBTQ vertices yielded soluble model compounds, which were analyzed by mass spectrometry and NMR spectroscopy. In contrast, methyl-substituted cages spontaneously crystallized as isostructural and highly porous solids with BET surface areas and pore volumes of up to 3426 m 2 g −1 and 1.82 cm 3 g −1 . Single crystal X-ray diffraction and sorption measurements revealed an intricate cubic arrangement of alternating micro-and mesopores in the range of 0.97-2.2 nm that are fine-tuned by the alkyl substituents at the BDBA linker. File list (8) download file view on ChemRxiv 2021_02_Ivanova_manuscript_ChemRxiv.pdf (3.17 MiB) download file view on ChemRxiv 2021_02_Ivanova_SI_ChemRxiv.pdf (9.00 MiB) download file view on ChemRxiv ek20_sq-finalcif.cif (3.79 MiB) download file view on ChemRxiv ek27_sq-finalcif.cif (2.93 MiB) download file view on ChemRxiv si30_sq-finalcif.cif (1.64 MiB) download file view on ChemRxiv 2Me_channel.mp4 (2.20 MiB) download file view on ChemRxiv 2Et_channel.mp4 (2.33 MiB) download file view on ChemRxiv 2nBu_channel.mp4 (2.64 MiB)

show abstract

“…Adapted with permission. [63] A modular library of diverse biphenyl, terphenyl, and higher linear linkers, based on Pd-catalyzed cross-coupling reactions, was investigated. d) MagGEL capsule.…”

Section: Research Activities In Smlmentioning

confidence: 99%

“…Consequently, the diversity of potential building blocks leads to an increasing demand for the design and synthesis of new [63] b) Proposed structure of SURMOF-2. Reproduced with permission.…”

Section: Research Activities In Smlmentioning

confidence: 99%

“…In this context, SML recently described a straightforward and efficient synthetic strategy for the preparation of linear ditopic functionalized organic linkers (Figure 4a). [63] A modular library of diverse biphenyl, terphenyl, and higher linear linkers, based on Pd-catalyzed cross-coupling reactions, was investigated. In addition to serve as useful mole cular bricks in the construction of different types of porous MOFs, the linkers exhibit functional side-groups-such as azide or alkyne moietiessuitable for postsynthetic modifications (PSM).…”

Section: Research Activities In Smlmentioning

confidence: 99%

See 1 more Smart Citation

Soft Matter Technology at KIT: Chemical Perspective from Nanoarchitectures to Microstructures

et al. 2019

Self Cite

View full text Add to dashboard Cite

Bioinspiration has emerged as an important design principle in the rapidly growing field of materials science and especially its subarea, soft matter science. For example, biological cells form hierarchically organized tissues that not only are optimized and designed for durability, but also have to adapt to their external environment, undergo self‐repair, and perform many highly complex functions. Being able to create artificial soft materials that mimic those highly complex functions will enable future materials applications. Herein, soft matter technologies that are used to realize bioinspired material structures are described, and potential pathways to integrate these into a comprehensive soft matter research environment are addressed. Solutions become available because soft matter technologies are benefitting from the synergies between organic synthesis, polymer chemistry, and materials science.

show abstract

Diverse Multi‐Functionalized Oligoarenes and Heteroarenes for Porous Crystalline Materials

Cited by 20 publications

References 48 publications

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Isoretikuläre Kristallisation von hochporösen kubischen kovalentorganischen Käfigverbindungen**

Soft Matter Technology at KIT: Chemical Perspective from Nanoarchitectures to Microstructures

Contact Info

Product

Resources

About