Photoresponsive frameworks: energy transfer in the spotlight

Martin, Corey R.; Park, Kyoung Chul; Corkill, Ryan E.; Kittikhunnatham, Preecha; Leith, Gabrielle A.; Mathur, Abhijai; Abiodun, Sakiru L.; Greytak, Andrew B.; Shustova, Natalia B.

doi:10.1039/d1fd00013f

Cited by 17 publications

(14 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8 The introduction of luminescent properties in MOFs can be achieved by incorporation of fluorescent bridging ligands and/or photoactive metal anions in their framework, that leads to infinite arrays of chromophores, analogous to what is observed for CPs. 9 Moreover, MOFs exhibit well defined crystalline structures with permanent porosity, structural diversity and tunability, and surface functionality that distinguishes them from luminescent organic CP sensors. Luminescent MOFs can respond to the encapsulation of various guest species within their structure's pores and therefore, display great potential for use in next generation sensing devices for in-field detection.…”

Section: Introductionmentioning

confidence: 99%

Detection of nitrophenols with a fluorescent Zr(iv) metal–organic framework functionalized with benzylamino groups

et al. 2022

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Detection of nitrophenols with a fluorescent Zr(iv) metal–organic framework functionalized with benzylamino groups

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Their often high emission intensity has been used in materials or applications such as sensors, − bioimaging, , and efficient upconversion materials. − The dynamic properties of the lowest singlet excited state have also been evaluated, and it is sufficiently long-lived [for instance, 1.88 ns for Zn(TCPP 4 – )] to allow for efficient energy- and electron-transfer processes. Indeed, singlet–singlet energy-transfer processes in MOFs and COFs are well documented, − as is energy migration. − In parallel, the presence of heavy atoms facilitates the population of the lowest energy triplet state, with many MOFs − and COFs showing intense phosphorescence with typical emission lifetimes in the microsecond scale. Triplet energy transfer , and energy migration (Figure ) throughout these materials have also been reported.…”

Section: Excited-state Properties Of Porphyrin-containing Mofs and Cofsmentioning

confidence: 99%

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Asselin

Harvey

2022

ACS Appl. Nano Mater.

View full text Add to dashboard Cite

Porphyrin-based materials are excellent chromophores because they strongly absorb visible light and their relatively low-energy lowest unoccupied molecular orbitals thermodynamically favor photoinduced electron transfer. They can generate charge-transfer excited states with and without cocatalyst(s) and ease energy transfer and ultrafast excitation energy migration. Combined with synthetic accessibility, these qualities make them ideal building blocks for porous metal− organic framework (MOF)-and covalent−organic framework (COF)-based photocatalysts to produce solar fuels. This review first describes the structures of the most common porphyrinic MOFs and COFs and their excited-state properties and semiconducting behavior as well as that of derived composites. The generally accepted mechanisms of formation of H 2 , CH 4 and derivatives, and N 2 are then reviewed, followed by the detailed examples of nano-MOFs and nano-COFs used for the said purpose: characteristic parameters such as rates of production, turnover numbers (TONs), turnover frequencies (TOFs), and apparent quantum efficiencies are described and compared. This shows that porphyrin-based MOFs and COFs are efficient solar-fuelproducing photocatalysts, with characteristics comparable to those of nonporphyrinic MOF and COF photocatalysts, although, on some occasions, the rates of production fall short of record values. Conversely, porphyrinic MOFs and COFs exhibit the greatest TONs and TOFs of any solar-fuel-producing MOFs or COFs but still face shortcomings concerning selectivity in CH 4 production because of the many possible side products. Importantly, while the best rate of photoproduction of solar fuels has been observed from nanoscale photocatalysts, there seem to be no drastic differences in the rate (within μmol −1 h −1 and mmol g −1 h −1 ) between nanoscale and microscale heterogeneous photocatalysts. This observation suggests that the more active sites are mostly located at or near the surface of the particles. Overall, nanosized porphyrin-based MOFs and COFs show rich and promising photocatalytic properties for generating solar fuels but still have room for improvement.

show abstract

“…Due to their toxicity and reactivity, expensive safety measures are required to handle, store, and transport these gases safely, thereby placing their usage in synthetic chemistry under strict regulations [7] . Herein, we probed metal‐organic frameworks (MOFs), [8–33] specifically their reversible gas adsorption and catalytic activity, to carry out chemical reactions in organic solvents. Thus, we explored the dual role of MOFs as a catalyst and carrier of reagents on the example of reactive gases.…”

Section: Introductionmentioning

confidence: 99%

A Metal‐Organic Framework (MOF)‐Based Multifunctional Cargo Vehicle for Reactive‐Gas Delivery and Catalysis

et al. 2022

Self Cite

View full text Add to dashboard Cite

The efficient delivery of reactive and toxic gaseous reagents to organic reactions was studied using metal‐organic frameworks (MOFs). The simultaneous cargo vehicle and catalytic capabilities of several MOFs were probed for the first time using the examples of aromatization, aminocarbonylation, and carbonylative Suzuki–Miyaura coupling reactions. These reactions highlight that MOFs can serve a dual role as a gas cargo vehicle and a catalyst, leading to product formation with yields similar to reactions employing pure gases. Furthermore, the MOFs can be recycled without sacrificing product yield, while simultaneously maintaining crystallinity. The reported findings were supported crystallographically and spectroscopically (e.g., diffuse reflectance infrared Fourier transform spectroscopy), foreshadowing a pathway for the development of multifunctional MOF‐based reagent‐catalyst cargo vessels for reactive gas reagents as an attractive alternative to the use of toxic pure gases or gas generators.

show abstract

Photoresponsive frameworks: energy transfer in the spotlight

Abstract: In this paper, spiropyran-containing metal- and covalent-organic frameworks (MOFs and COFs, respectively) are probed as platforms for fostering photochromic behavior in solid-state materials while simultaneously promoting directional energy transfer (ET)....

Cited by 17 publications

References 71 publications

Detection of nitrophenols with a fluorescent Zr(iv) metal–organic framework functionalized with benzylamino groups

Detection of nitrophenols with a fluorescent Zr(iv) metal–organic framework functionalized with benzylamino groups

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

A Metal‐Organic Framework (MOF)‐Based Multifunctional Cargo Vehicle for Reactive‐Gas Delivery and Catalysis

Contact Info

Product

Resources

About