Synthesis of a tetraphenylethylene-based metal-organic framework as the luminescent sensor for selective sensing of Cr2O72− in aqueous solution

Huai, Ranran; Xu, Mengzhen; Dou, Ying; Wang, Zhaojie; Xue, Zengmin; Zhang, Yue; Lv, Huaxin; Qin, Likang; Zhang, Daopeng; Zhou, Zhen; Yang, Lu

doi:10.1016/j.inoche.2021.108550

Cited by 7 publications

(6 citation statements)

References 36 publications

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“…The solid-state emission in L1 -Eu MOF blue-shifted to 397 nm from 414 nm of free L1 (Figure S19). Thus, the coplanar structure of L1 decreases to adapt the coordination as the characteristics of AIE ligands in MOFs. , The twisted structure changes the π-conjugation of L1 and results in the blue-shift emission. Similarly, the absorption peak of L1 at 319 nm shifts to 270 nm in L1 -Eu MOF (Figure S20).…”

Section: Results and Discussionmentioning

confidence: 99%

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Ligand Energy Staff Gauge for Antenna Effect Study within Metal–Organic Frameworks

Xie

Zhang

et al. 2023

J. Phys. Chem. C

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Revealing the structure–optical property relationship of aggregation-induced emission (AIE) species (AIEgens) and achieving the synergy between AIE and antenna effect are challenging. Herein, we study the emission behaviors of three AIE ligands with tetraphenyl structures, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (L1), 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (L2), and 1,1,2,2-tetrakis(4-carboxyphenyl)ethylene (L3), and find their ladder-shaped emission wavelength. In combination with terephthalic acid (L0), we construct a staff gauge from L0 to L3 to realize different sensitization for Ln3+ from the sensitization of both Eu3+ and Tb3+ to single Eu3+ and then to non-sensitization. We proposed the threshold value of 5000 cm–1 for complete sensitization from the different optical behaviors and energy levels of the lanthanide metal–organic frameworks (Ln-MOFs). Coplanar degree of L1–L3 is proposed to explain their optical behaviors and different sensitization. Thus, we revealed the connection among the energy levels, emission wavelength, and their effect on antenna effect for AIE ligands. L1-Eu MOF exhibits a dual emission with a porous property and is used for ratiometric fluorescent detection and removal of F–.

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Section: Results and Discussionmentioning

confidence: 99%

“…Thus, the coplanar structure of L1 decreases to adapt the coordination as the characteristics of AIE ligands in MOFs. 26,41 The twisted structure changes the πconjugation of L1 and results in the blue-shift emission.…”

Section: Optical Property Of L1-eu Mofmentioning

confidence: 99%

Ligand Energy Staff Gauge for Antenna Effect Study within Metal–Organic Frameworks

Xie

Zhang

et al. 2023

J. Phys. Chem. C

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“…Derivatives of TPE have been shown to undergo AIE due to restriction of intramolecular motions of the phenyl rings or the existence of a conical intersection in the solid state. − Because TPE derivatives are AIE-active and a rigid MOF can activate photoluminescence of TPEs via MCIE, , we aimed to study the effect of defects on photophysical properties using a TCPE 4– -based MOF as a model system (see the Supporting Information or SI Section 2a,b for synthetic details). This linker has been previously employed to prepare frameworks from Zn, , Cd, La, Nd, and UO 2 , , but its incorporation into a Zr-based MOF (with she topology) was only reported during the preparation of this manuscript . A series of Zr-TCPE MOFs were initially synthesized at 120 °C for 48 h using ZrCl 4 as a metal precursor, formic acid (FA) as a modulator, H 2 O to facilitate Zr 6 cluster formation, and N , N -dimethylformamide (DMF) as a solvent (Figure a and SI Section 2c).…”

Section: Resultsmentioning

confidence: 99%

Enhancing Dynamic Spectral Diffusion in Metal–Organic Frameworks through Defect Engineering

et al. 2023

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The crystal packing of organic chromophores has a profound impact on their photophysical properties. Molecular crystal engineering is generally incapable of producing precisely spaced arrays of molecules for use in photovoltaics, light-emitting diodes, and sensors. A promising alternative strategy is the incorporation of chromophores into crystalline metal−organic frameworks (MOFs), leading to matrix coordination-induced emission (MCIE) upon confinement. However, it remains unclear how the precise arrangement of chromophores and defects dictates photophysical properties in these systems, limiting the rational design of well-defined photoluminescent materials. Herein, we report new, robust Zr-based MOFs constructed from the linker tetrakis(4-carboxyphenyl)ethylene (TCPE 4− ) that exhibit an unexpected structural transition in combination with a prominent shift from green to blue photoluminescence (PL) as a function of the amount of acid modulator (benzoic, formic, or acetic acid) used during synthesis. Time-resolved PL (TRPL) measurements provide full spectral information and reveal that the observed hypsochromic shift arises due to a higher concentration of linker substitution defects at higher modulator concentrations, leading to broader excitation transfer-induced spectral diffusion. Spectral diffusion of this type has not been reported in a MOF to date, and its observation provides structural information that is otherwise unobtainable using traditional crystallographic techniques. Our findings suggest that defects have a profound impact on the photophysical properties of MOFs and that their presence can be readily tuned to modify energy transfer processes within these materials.

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“…[40][41][42][43][44] Because TPE derivatives are AIE-active and a rigid MOF can activate photoluminescence of TPEs via MCIE, 16 we aimed to study the effect of defects on photophysical properties using a TCPE 4− -based MOF as a model system (see Supporting Information or SI Section 2a-b for synthetic details). This linker has been previously employed to prepare frameworks from Zn, 16,24 Cd, 16 La, Nd, 23 and UO2, 21,22 but its incorporation into a Zr-based MOF (with she topology) was only reported during the preparation of this manuscript. 45 A series of Zr-TCPE MOFs were initially synthesized at 120 °C for 48 h using ZrCl4 as a metal precursor, formic acid (FA) as a modulator, H2O to facilitate Zr6 cluster formation, and N,N-dimethylformamide (DMF) as a solvent (Figure 1a, SI Section 2c).…”

Section: Resultsmentioning

confidence: 99%

“…19 Last, many photoluminescent MOFs degrade or suffer from quenched fluorescence upon exposure to water, limiting their application under realistic conditions. [20][21][22][23][24] Ideally, one would be able to dial in the desired photophysical properties of a chromophore confined within a stable MOF, streamlining the preparation of new photoluminescent materials with tailorable properties.…”

Section: Introductionmentioning

confidence: 99%

Enhancing Dynamic Spectral Diffusion in Metal-Organic Frameworks Through Defect Engineering

Halder

Bain

Oktawiec³

et al. 2022

Preprint

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The crystal packing of organic chromophores has a profound impact on their photophysical properties. Molecular crystal engineering is generally incapable of producing precisely spaced arrays of molecules for use in photovoltaics, light-emitting diodes, and sensors. A promising alternative strategy is the incorporation of chromophores into crystalline metal-organic frameworks (MOFs), leading to matrix coordination-induced emission (MCIE) upon confinement. However, it remains unclear how the precise arrangement of chromophores and defects dictates photophysical properties in these systems, limiting the rational design of well-defined photoluminescent materials. Herein, we report new, robust Zr-based MOFs constructed from the linker tetrakis(4-carboxyphenyl)ethylene (TCPE4−) that exhibit an unexpected structural transition in combination with a prominent shift from green to blue photoluminescence (PL) as a function of the amount of acid modulator (benzoic, formic, or acetic acid) used during synthesis. Time-resolved PL (TRPL) measurements provide full spectral information and reveal that the observed hypsochromic shift arises due to a higher concentration of linker substitution defects at higher modulator concentrations, leading to broader excitation transfer-induced spectral diffusion. Spectral diffusion of this type has not been reported in a MOF to date, and its observation provides structural information that is otherwise unobtainable using traditional crystallographic techniques. Our findings suggest that defects have a profound impact on the photophysical properties of MOFs, and that their presence can be readily tuned to modify energy transfer processes within these materials.

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Synthesis of a tetraphenylethylene-based metal-organic framework as the luminescent sensor for selective sensing of Cr2O72− in aqueous solution

Cited by 7 publications

References 36 publications

Ligand Energy Staff Gauge for Antenna Effect Study within Metal–Organic Frameworks

Ligand Energy Staff Gauge for Antenna Effect Study within Metal–Organic Frameworks

Enhancing Dynamic Spectral Diffusion in Metal–Organic Frameworks through Defect Engineering

Enhancing Dynamic Spectral Diffusion in Metal-Organic Frameworks Through Defect Engineering

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