A Multicenter Metal–Organic Framework for Quantitative Detection of Multicomponent Organic Mixtures

Open AccessCCS ChemistryCOMMUNICATION3 Oct 2022A Multicenter Metal–Organic Framework for Quantitative Detection of Multicomponent Organic Mixtures Zongsu Han, Kunyu Wang, Yinlin Chen, Jiangnan Li, Simon J. Teat, Sihai Yang, Wei Shi and Peng Cheng Zongsu Han Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071 Google Scholar More articles by this author , Kunyu Wang Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071 Google Scholar More articles by this author , Yinlin Chen Department of Chemistry, The University of Manchester, Manchester M13 9PL Google Scholar More articles by this author , Jiangnan Li Department of Chemistry, The University of Manchester, Manchester M13 9PL Google Scholar More articles by this author , Simon J. Teat Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 Google Scholar More articles by this author , Sihai Yang Department of Chemistry, The University of Manchester, Manchester M13 9PL Google Scholar More articles by this author , Wei Shi *Corresponding author: E-mail Address: [email protected] Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071 Google Scholar More articles by this author and Peng Cheng Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202101642 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Instant recognition and quantification of multicomponent organic mixtures, especially the ones with similar characteristics, remains a key challenge in the chemical industry. Although luminescence sensing is considered a rapid and facile method for the detection of various chemical substances, the simultaneous and quantitative detection of three or more components has not yet been achieved. Herein, we report a rationally designed white-light-emitting metal–organic framework (MOF) [email protected], and demonstrate its application in the simultaneous discrimination of multicomponent organic mixtures. The concentration of each component in the mixture can be obtained based on the correlation of the emission intensity changes in 10 s, enabling instant and quantitative analysis. The sensing mechanism of this complex system was studied in detail. This study paves the way for the rapid detection of multicomponent mixtures using MOF-based luminescent materials with multiemission centers. Download figure Download PowerPoint Introduction Instant and quantitative detection of multicomponent chemical mixtures is highly important not only in industry for monitoring chemical reaction processes but also in public life for sensing the quality of water, food, and air. For example, isomer mixture presents and often dominates the chemical industry, such as in pharmaceuticals, dyestuff, and pesticide production.1,2 Generally, isomers have distinct properties.3,4 In medicine, toxicity, pathogenicity, and carcinogenicity vary among different isomers.5–7 However, the homologous structures and physical properties of isomers render their recognition highly challenging,8–10 necessitating complex instrumentation, complicated pretreatment, and toxic reagents, with a delayed response. As a promising alternative for isomer detection, luminescent sensing materials have attracted great interest because of their high selectivity, high sensitivity, and fast response. However, most of the target systems have been limited to single species or two-component isomers, and the quantitative discrimination of multicomponent isomer mixtures has not been reported thus far,11–13 despite its being crucial for practical applications (Schemes 1a–1c and Supporting Information Table S1). Scheme 1 | The strategy for detection of multicomponent mixtures. (a) Conventional work for the detection of one analyte in mixtures. (b) Our strategy for the detection of multicomponent mixtures. (c) Schematic illustration of the detection of multicomponent mixture by [email protected] Download figure Download PowerPoint Metal–organic frameworks (MOFs), which are high-dimensional coordination compounds composed of metal nodes coordinated with organic linkers, have immense potential for the detection of chemical species because of their porous, designable structures.14–18 Recently, hierarchically porous MOFs have garnered considerable attention because of their precise control of various hierarchy variables, including their porosity, structure, components, and morphology, and their suitability for the study of host–guest chemistry.19,20 Various chemical species, such as volatile organic compounds, persistent organic pollutants, chiral molecules, and micromolecular biomarkers, have been studied by MOF-based sensing materials.21–24 Compared to conventional sensing materials, the luminescent signals of MOFs can be fine-tuned through the regulation of the coordination framework as well as the pore structure to match the target system in structure and/or energy level for realizing a high-performance sensing function.25–27 In this study, we report a triple-emission white-light MOF [email protected] of {[Eu(H2O)9]0.120[Tb(H2O)9]0.120 [Mg(H2O)6]11.640[Mg12(TDPAT)8(H2O)24]}·24DMF (H6TDPAT = 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine, DMF = N,N-dimethylformamide) synthesized by the introduction of red- and green-emitting Eu3+ and Tb3+ ions with optimized doping contents in the pores of a blue-emitting MOF NKU-102 of {[Mg(H2O)6]12[Mg12(TDPAT)8(H2O)24]}·24DMF ( Supporting Information Figure S1). As one of the representative isomers, diaminobenzenes, which are extensively utilized in industry, agriculture, and public life, are selected as the target system28–30: o-diaminobenzene is mainly used as a pesticide and bactericide; m-diaminobenzene is an essential raw material for dyestuff, medicine, and rubber; p-diaminobenzene, the most poisonous isomer, is a crucial intermediate of dyestuff and rubber additives. Moreover, m-diaminobenzene and p-diaminobenzene are carcinogens. Owing to the large difference in the quenching efficiencies of the different emission centers, [email protected] turns its white color to dark purple, white, and brilliant blue in 10 s with the addition of o-, m-, and p-diaminobenzene under ultraviolet light, respectively ( Supporting Information Figure S2). Importantly, the concentrations of different isomers in the mixtures can be quantified based on the luminescence of [email protected] This is the first MOF-based luminescence sensor for the rapid and simultaneous discrimination of three-component isomer mixtures. Results and Discussion Single crystals of NKU-102 were synthesized through the solvothermal reaction of MgCl2·6H2O and H6TDPAT in DMF with hydrochloric acid. NKU-102 crystallized in the cubic space group Fm-3m ( Supporting Information Table S2). An asymmetric unit included crystallographically independent 1/4 Mg2+ ions, 1/6 ligands, and 1/2 coordinative water molecules. Each Mg2+ ion was coordinated by six oxygen atoms from four ligands and two water molecules, and each ligand connected to six Mg2+ ions. As shown in Figures 1a–1d, three different types of cages were formed: cage (1) with a side length of 20.5 Å and square-window side length of 7.7 Å, cage (2) with a side length of 15.3 Å and square-window side length also of 7.7 Å, and cage (3) with a side length of 18.0 Å and triangular-window side length of 7.7 Å. The stoichiometry of the cages was 1:1:2. Topologically, when considering the Mg2+ ions as vertices and the ligands as hexagons, cages (1) and (3) could be simplified into two Archimedean solids, a truncated octahedron and truncated tetrahedron, respectively. Cage (2) was composed of Mg2+ ions and the isophthalic moieties of the hexacarboxylic ligand, generating a cuboctahedron cage based on eight triangles and six squares. These three cages were combined to give a (4-c)3(6-c)2 network with a Schläfli symbol of {43·612}2{46}3. The formation of the cage-based framework was attributed to the utilization of the flexible hexacarboxylic ligand and S4-symmetry Mg2+ node. In NKU-102, the hexacarboxylic ligand featured high flexibility and adaptability during the coordination, while the Mg2+ ion adopted a limited coordination number and confined geometry that drove the ligand into cage assemblies. Such a design principle may provide prospects for the synthesis of novel cage-based MOFs. Compared to other MOFs in the (4,6)-c topology, namely iac, fsn, she, soc, and cor,31–35 NKU-102 features diverse pore environments. Such a hierarchically porous structure can facilitate mass transfer and accommodate multiple binding sites for guest molecules.23 Cage-based MOFs with hexacarboxylic ligands have been rarely reported. For instance, Ma and co-workers36 reported a highly stable MOF, JUC-1000, which contained three types of cages, significantly facilitating the CO2 adsorption and transformation. Though both the ligands can be simplified into a planar hexagon, the varying connectivity and directionality of the metal clusters lead to different topologies and functions of the resultant MOFs. In NKU-102, the various pore environments not only provide multiple sites to accommodate the Tb3+ and Eu3+ ions, but also facilitate the mass transfer of the analytes. It is noted that NKU-102 contained 24 connected supermolecular rhombicuboctahedral cages, which were based on 12 Mg nodes and 24 isophthalic acids. These cages, as supermolecular building blocks, were interconnected through three connected nodes derived from the ligand, resulting in a (3,24)-c network with rht topology.37 Interestingly, most rht MOFs were based on Cu/Zn paddlewheels, and rht MOFs with mononuclear metal nodes have not been reported.38 Figure 1 | (a) Framework structure and topology of NKU-102. (b–d) Three different cages (Atom code: C, gray; N, blue; O, red; Mg, turquoise; H omitted for clarity). Download figure Download PowerPoint [email protected] was synthesized through cation exchange in DMF solution with equimolar Eu(III) and Tb(III) ions. Powder X-ray diffraction (PXRD) patterns confirm that NKU-102 and [email protected] are isostructural ( Supporting Information Figure S3). Thermal gravimetric analysis indicates continuous weight loss for both NKU-102 and [email protected] in the 40–250 °C temperature range due to the loss of water and DMF molecules ( Supporting Information Figure S4). Moreover, the infrared spectra of [email protected] do not differ from those of NKU-102 ( Supporting Information Figure S5), suggesting retention of the coordination structure during the ion-exchange process. Sensing experiments were performed at an excitation wavelength of 336 nm. The time-dependent luminescence intensities of [email protected] were stable ( Supporting Information Figure S6). o-, m-, and p-diaminobenzene DMF solutions were added dropwise to the DMF suspension of [email protected], respectively, with a rapid response (Figures 2a and 2b). The quenching of the emission peaks at 357, 545, and 615 nm by o-, m-, and p-diaminobenzene followed the nonlinear Stern–Volmer (S–V) equation.39 The quenching constant (KSV) values were 189, 8, and 23,408 M−1 at 357 nm based on the fitting results with equation I0/I = a exp(k[C]) + b (a, b, and k are constants), depicted in Figures 2c–2e. At concentrations below 1.2, 2.0, and 0.4 mM, linear fit with equation I0/I = KSV[C] + b yields KSV values of 360, 117, and 4530 M−1 for o-, m-, and p-diaminobenzene, respectively ( Supporting Information Figure S7). This result suggests that the interaction of [email protected]KU-102 with diaminobenzene isomer differs from each other; therefore, it can be utilized as a highly selective sensing material for these isomers, in which p-diaminobenzene has the strongest luminescence response. Figure 2 | (a) Visual luminescent responses of [email protected] towards o-, m- and p-diaminobenzene. (b) Time-dependence of the intensities of [email protected] with addition of diaminobenzene mixture. (c–e) Luminescence intensities of [email protected] DMF dispersions with incremental addition of o-, m-, and p-diaminobenzene, respectively. RSD stands for relative standard deviation. Download figure Download PowerPoint Based on the different quenching performances of the three emission peaks of [email protected], the concentrations of o-, m-, and p-diaminobenzene in the isomer mixture can be calculated (details in Supporting Information). If two concentrations are known (one independent variable), fitting equation ln(I0/I) follows a linear relationship with the varied concentrations, and working curves can be generated. If one concentration or the total concentration is known (two independent variables), ln(I0/I) follows a quadratic relationship with the other concentrations, and “working surfaces” can be generated. If all the concentrations are unknown (three independent variables), ln(I0/I) follows a functional relationship with the concentrations, and “working spaces” can be generated. The original data and the corresponding fitting results are provided in Supporting Information Figures S8–S10 and Table S3. These fitting equations are applicable under different situations, which is suitable for the practical detection of multicomponent mixtures. To simplify the mathematical process, the data processing was programmed by Python and provided as the Supplementary program ( Supporting Information Figure S11). To obtain the triplet state energy levels of the ligand for investigating the luminescence-sensing mechanism, [email protected] was synthesized. Solid-state UV–vis absorption spectrum of the ligand at room temperature ( Supporting Information Figure S12) and phosphorescence spectrum of [email protected] at 77 K ( Supporting Information Figure S13) were measured, and the energy levels of the singlet state (22,026 cm−1) and triplet state (35,088 cm−1) were obtained. The energy gap of 13,062 cm−1 between the singlet and triplet states of H6TDPAT was greater than 5000 cm−1, indicating that the intersystem-crossing process was effective.39 The energy gaps of 4526 and 1626 cm−1 between the triplet state of H6TDPAT and 5D0 for Eu3+/5D4 for Tb3+ ions, respectively, were both greater than 1500 cm−1 ( Supporting Information Figure S14), indicating that both Eu3+ and Tb3+ ions can be sensitized by H6TDPAT.39–41 Furthermore, the quenching mechanism was examined (Figure 3a). PXRD patterns of [email protected] after soaking in o-, m-, and p-diaminobenzene were almost invariable, indicating no structural destruction during the sensing process ( Supporting Information Figure S3). Infrared spectra of [email protected] after soaking in o-, m-, and p-diaminobenzene were also invariable, indicating the retention of the framework structure ( Supporting Information Figure S15). According to the calculation results of the energy levels, the LUMOs of o-, m-, and p-diaminobenzene were obviously higher than that of H6TDPAT ( Supporting Information Table S4), suggesting the absence of the photoinduced electron transfer process in luminescent quenching.11,13 There were obvious overlaps in the UV–vis spectra of the diaminobenzenes and [email protected], indicating that competitive absorption (CA) of the excitation light was responsible for luminescence quenching ( Supporting Information Figure S16).13 At 336-nm excitation, the [email protected] ligand effectively absorbed UV light ( Supporting Information Figure S16a). The absorption at 336 nm by p-diaminobenzene was approximately 33 times that of o-diaminobenzene (Figure 3b and Supporting Information Figure S16b), inducing strong quenching by p-diaminobenzene and weak quenching by o-diaminobenzene. m-diaminobenzene hardly absorbed UV light at 336 nm, causing almost no change in the luminescence. Hence, the quenching of [email protected] based on the CA mechanism followed the order p-diaminobenzene > o-diaminobenzene > m-diaminobenzene. Figure 3 | Sensing mechanism of [email protected] (“s”, “m,” and “w” denote strong, medium, and weak interactions, respectively) (a). UV–vis absorption intensities of o-, m- and p-diaminobenzene at 336 nm (red bar), and the overlap integral areas between UV–vis spectra of o-, m- and p-diaminobenzene and emission spectrum of [email protected] (blue bar) (b). Quantum yield changes with the additions of o-, m- and p-diaminobenzene (c). Luminescence lifetime results of [email protected] DMF suspensions with the additions of o-, m- and p-diaminobenzene at 357 nm (d), 545 nm (e), and 615 nm (f). Download figure Download PowerPoint In addition, the emission spectrum of [email protected] and the UV–vis spectra of diaminobenzenes showed that there was an obvious overlap of the ligand emission with p-diaminobenzene, small overlap with o-diaminobenzene, and negligible overlap with m-diaminobenzene, suggesting that Förster resonance energy transfer (FRET) existed and contributed to the quenching by p-diaminobenzene and o-diaminobenzene ( Supporting Information Figure S17).42 The overlap integral area of [email protected] and p-diaminobenzene was approximately 35 times that of o-diaminobenzene (Figure 3b). Hence, the quenching of [email protected] based on the FRET mechanism followed the same order as the CA mechanism. The quantum yield of [email protected] decreased with the addition of o-, m-, and p-diaminobenzene at different efficiencies as per the following order: p-diaminobenzene > o-diaminobenzene > m-diaminobenzene (Figure 3c and Supporting Information Table S5). This reflects the degree of reduction in the energy absorption through the CA mechanism and the reduced energy release through the FRET mechanism for [email protected] In addition, the luminescence lifetimes of [email protected] in DMF suspensions decreased with the addition of o-, m-, and p-diaminobenzene (Figures 3d–3f and Supporting Information Figure S18 and Table S6), suggesting that the quenching process is dynamic, facilitating nonradiative transitions to the ground state.39 Energy transfer processes based on the “antenna effect” and the interaction of Eu3+ and Tb3+ played a key role in the different luminescence quenching performances of the TDPAT6−, Eu3+, and Tb3+ centers.13,43 Reduced excitation energy to the ligand by diaminobenzene resulted in quenching of the ligand and further reduced energy transfer from the ligand to the lanthanide ions, inducing the quenching of Eu3+ and Tb3+. Energy transfer from Tb3+ ions to Eu3+ ions in [email protected] was confirmed by the emission spectrum excited at 488 nm, which is one of the characteristic emission wavelengths of the Tb3+ ion ( Supporting Information Figure S19). The quantum yield ratio of ligand:Tb3+:Eu3+ was about 3.6:1.3:1, indicating higher energy transfer efficiency from the ligand to Tb3+ than that to Eu3+ ( Supporting Information Figure S20). Eu3+ and Tb3+ ion emissions differed with equal concentrations of diaminobenzene isomers, based on the unequal energy transfer efficiencies. Based on the above mechanism, the o-diaminobenzene quenched [email protected] by FRET and CA processes, inducing the nearly equal quenching of the TDPAT6−, Eu3+ and Tb3+ centers, giving a dark purple luminescence; the m-diaminobenzene quenched [email protected] by a limited CA process, inducing the weak quenching of the TDPAT6−, Eu3+ and Tb3+ centers, giving a near-white luminescence; the p-diaminobenzene quenched [email protected] by strong FRET and CA processes, inducing the high-degree quenching of the TDPAT6− center and the low-degree quenching of the Eu3+ and Tb3+ centers, to give a brilliant blue luminescence. Conclusion We developed a multicenter MOF [email protected] with white-light emission for the visual and quantitative recognition of isomer mixtures ( Supporting Information Table S7). The programmable luminescent responses of the multiemission centers enable the facile determination of the concentration of isomers in the mixtures with fast responses in 10 s. CA of the excitation photons and the FRET process play a key role in governing the sensing function. This study not only provides a powerful platform for instant detection of the targeted chemical mixtures (isomers in this study) but also paves the way for the development of visual and quantitative sensors for realistic chemical mixtures, which can be extensively applied in industry, agriculture, and public life. Supporting Information Supporting Information is available and includes experimental procedures, methods, basic characterizations, and luminescence spectra. The calculation program is available from corresponding author. Conflict of Interest There is no conflict of interest to report. Funding Information This work was supported by the National Natural Science Foundation of China (grant nos. 21931004 and 21861130354), the Natural Science Foundation of Tianjin (grant no. 18JCJQJC47200), and the Ministry of Education of China (grant no. B12015). 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 4Issue 10Page: 3238-3245Supporting Information Copyright & Permissions© 2022 Chinese Chemical SocietyKeywordsmetal–organic frameworkisomermulticenter emissionsensing materialmulticomponent mixtureAcknowledgmentsS.Y. and W.S. acknowledge the receipt of a Royal Society Newton Advanced Fellowship (grant no. NAFR1180297). This research utilizes the resources of Beamline 12.2.1 at the Advanced Light Source, which is a DOE scientific user facility at Lawrence Berkeley Laboratory under contract no. DE-AC02-05CH11231. Z.H. is thankful to Houhua He for the development of the fitting software. Downloaded 1,135 times PDF downloadLoading ...