J-dimer emission in interwoven metal–organic frameworks

Newsome, Wesley; Chakraborty, Arnab; Ly, Richard T.; Pour, Gavin S.; Fairchild, David C.; Morris, Amanda J.; Uribe‐Romo, Fernando J.

doi:10.1039/d0sc00876a

Cited by 15 publications

(11 citation statements)

References 35 publications

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“…To verify our speculation about the ACQ effect in UiO-68-NTMB and UiO-68-NSMB and to improve the quantum efficiency, a mixed-linker strategy was employed, where a nonemissive linker, 2′,5′-dimethyl-[1,1′:4′, 1″-terphenyl]-4,4″-dicarboxylic acid ( d TPDC), was used along with the emissive NTMB and NSMB to increase the distances between the emissive linkers. ,, For d TPDC, its HOMO (LUMO) is much lower (higher) than those of the six emissive linkers; therefore, no charge/energy transfer will occur between d TPDC and the emissive linkers (Figure S5). Mixed-linker MOFs were thus prepared using the same method as for pure linker MOFs (Table S1), where the ratio of L and d TPDC varies from 1:1 to 1:2, 1:5, and 1:10.…”

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confidence: 99%

Linker Engineering toward Full-Color Emission of UiO-68 Type Metal–Organic Frameworks

Ren

Zhou

et al. 2021

J. Am. Chem. Soc.

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Luminescent metal–organic frameworks (LMOFs) demonstrate strong potential for a broad range of applications due to their tunable compositions and structures. However, the methodical control of the LMOF emission properties remains a great challenge. Herein, we show that linker engineering is a powerful method for systematically tuning the emission behavior of UiO-68 type metal–organic frameworks (MOFs) to achieve full-color emission, using 2,1,3-benzothiadiazole and its derivative-based dicarboxylic acids as luminescent linkers. To address the fluorescence self-quenching issue caused by densely packed linkers in some of the resultant UiO-68 type MOF structures, we apply a mixed-linker strategy by introducing nonfluorescent linkers to diminish the self-quenching effect. Steady-state and time-resolved photoluminescence (PL) experiments reveal that aggregation-caused quenching can indeed be effectively reduced as a result of decreasing the concentration of emissive linkers, thereby leading to significantly enhanced quantum yield and increased lifetime.

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confidence: 99%

Linker Engineering toward Full-Color Emission of UiO-68 Type Metal–Organic Frameworks

Ren

Zhou

et al. 2021

J. Am. Chem. Soc.

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“… 32 , 33 For instance, it was found that the stiffening of luminophores in networks increases their fluorescence intensity because of decreased vibrational decay. Furthermore, the precise spatial fixation of fluorophores within a lattice can significantly influence the fluorescence properties and lead to interesting effects like J dimer emission 34 or multiemission. 35 , 36 Also, phenomena like charge and energy transfer, known from classical coordination chemistry, were observed.…”

Section: Introductionmentioning

confidence: 99%

“…Since then, different strategies were used to integrate fluorescent moieties into MOFs especially for sensing applications. , For instance, it was found that the stiffening of luminophores in networks increases their fluorescence intensity because of decreased vibrational decay. Furthermore, the precise spatial fixation of fluorophores within a lattice can significantly influence the fluorescence properties and lead to interesting effects like J dimer emission or multiemission. , Also, phenomena like charge and energy transfer, known from classical coordination chemistry, were observed. , In addition to pure ligand-based fluorescence, MOFs containing d 10 ions often exhibit metal-to-ligand (MLCT) and ligand-to-metal charge transfer (LMCT) . Alternatively, fluorophores can be introduced into the pore system, which can lead to interesting emission properties .…”

Section: Introductionmentioning

confidence: 99%

Integration of Fluorescent Functionality into Pressure-Amplifying Metal–Organic Frameworks

et al. 2021

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The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal–organic frameworks (MOFs). In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption (NGA) and pressure amplification (PA) are the more recent discoveries in this field initially observed in the cubic DUT-49 framework. In recent years, the structural contraction was monitored by physisorption, X-ray diffraction, nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) techniques, providing only limited information about the electronic structure of the ligand. In this work, we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT-140(M) (M-Cu, Co, Zn), crystallizing in the space group Fm 3̅ m . DUT-140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m 2 g –1 and a pore volume of 2.59 cm 3 g –1 . Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using postsynthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu), spectroscopic and computational methods were used to study the light absorption properties.

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“…32,33 For instance, it was found that the stiffening of luminophores in networks increases their fluorescence intensity because of decreased vibrational decay. Furthermore, the precise spatial fixation of fluorophores within a lattice can significantly influence the fluorescence properties and lead to interesting effects like J dimer emission 34 or multi emission. 35,36 Also, phenomena like charge and energy transfer, known from classical coordination chemistry, were observed.…”

Section: Introductionmentioning

confidence: 99%

Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

Walenszus¹,

Evans²,

Bon³

et al. 2021

Preprint

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The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal-organic frameworks. In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption and pressure amplification is one of the more recent discoveries in this field, initially observed in the cubic DUT-49 framework. In recent years the structural contraction was monitored by physisorption, X‑ray diffraction, NMR and EPR techniques, providing only limited information about the electronic structure of the ligand. In this work we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT‑140(M) (M - Cu, Co, Zn) crystalizing in space group. DUT‑140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2g-1 and a pore volume of 2.59 cm3g-1. Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using post-synthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu) spectroscopic and computational methods were used to study the light absorption properties.

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J-dimer emission in interwoven metal–organic frameworks

Abstract: J-dimer emission is an emergent property that occurs when pairs of ground-state fluorophores associate within multivariate MOFs producing tunable red shifted emission.

Cited by 15 publications

References 35 publications

Linker Engineering toward Full-Color Emission of UiO-68 Type Metal–Organic Frameworks

Linker Engineering toward Full-Color Emission of UiO-68 Type Metal–Organic Frameworks

Integration of Fluorescent Functionality into Pressure-Amplifying Metal–Organic Frameworks

Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

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