Positive cooperative binding, a phenomenon prevalent in biological processes, holds great appeal for the design of highly sensitive responsive molecules and materials. It has been demonstrated that ...metal–organic frameworks (MOFs) can show positive cooperative adsorption to the benefit of gas separation, but potential binding cooperativity is largely ignored in the study of sensory MOFs. Here, we report the first demonstration of positive cooperative protonation of a MOF and the relevant pH response in fluorescence and proton conduction. The MOF is built of Zr–O clusters and bipyridyl-based tetracarboxylate linkers and has excellent hydrolytic stability. It shows a unique pH response that features two synchronous abrupt turn-off and turn-on fluorescent transitions. The abrupt transitions, which afford high sensitivity to small pH fluctuations, are due to cooperative protonation of the pyridyl sites with a Hill coefficient of 1.6. The synchronous dual-emission response, which leads to visual color change, is ascribable to proton-triggered switching between (n, π*) and (π, π*) emissions. The latter emission can be quenched by electron donating anion-dependent through photoinduced electron transfer and ground-state charge transfer. Associated with cooperative protonation, the proton conductivity of the MOF is abruptly enhanced at low pH by two orders, but overhigh acid concentration is adverse because excessive anions can interrupt the conducting networks. Our work shows new perspectives of binding cooperativity in MOFs and should shed new light on the development of responsive fluorescent MOFs and proton conductive materials.
Due to its great relevance to environmental, biological, and chemical processes, the precise detection of pH or acidic/basic species is an ongoing and imperative need. In this context, pH-sensitive ...luminescent systems are highly desired. We reported a three-dimensional Zn(II) MOF synthesized from a bipyridyl-tetracarboxylic ligand and composed of 4-fold interpenetrated diamond frameworks. Because the steric hindrance in the ligand prevents metal coordination with the pyridyl group, the MOF features free basic N sites accessible to the small H
ions, which renders pH responsivity. The aqueous dispersion exhibits an abrupt, high-contrast, and reversible on-off fluorescence transition in the narrow pH range of 5.4-6.2. The sensitive bistable system can be used for the precise monitoring of pH within the range and for use as a pH-triggered optical switch. The responsive mechanism through pyridyl protonation is collaboratively supported by data fitting, absorption spectra, and molecular orbital calculations. In particular, spectral and theoretical analyses reveal the destruction of n → π* transitions and the appearance of intramolecular charge-transfer transitions upon pyridyl protonation. Moreover, by virtue of the pH-responsive fluorescence, the MOF shows appealing sensing performance for the detection of 3-nitropropionic acid, a major mycotoxin in moldy sugar cane.
The recently emerging vinylene-linked covalent organic frameworks (VCOFs) stand out from other COFs with exceptional chemical stability and favorable light-emitting properties, promising sensing ...applications for acids/bases or in strong acidic/basic conditions. Here we systematically investigated the reversible color and fluorescent response of a VCOF functionalized with pyridyl groups to acids/pH. The COF was synthesized with a record surface area for VCOFs and shows reversible hydrochromic and acidochromic behaviors and concomitant fluorescence quenching. The mechanisms were probed with systematical experimental comparison with relevant COFs and model molecules in combination with orbital analysis. The response is related to significant electronic changes in the ground and photoexcited states as a result of protonation or hydrogen bonding at pyridyl sites. The COF in aqueous dispersion displays a reversible fluorescence transition with pH change, which follows the Hill equation for multisite protonation. The COF-modified test paper shows immediate and remarkable color change and fluorescence turn-off/on when alternately exposed to HCl and NH3 gases. The work illustrates the great potential of developing highly robust sensory COFs through the vinylene approach.
The assembly of two tripyridinium‐tricarboxylate ligands and different metal ions leads to seven isostructural MOFs, which show novel 2D→2D supramolecular entanglement featuring catenane‐like ...interlocking of tricyclic cages. The MOFs show tripyridinium‐afforded and metal‐modulated photoresponsive properties. The MOFs with d10 metal centers (1‐Cd, 1‐Zn, 2‐Cd, 2‐Zn) show fast and reversible photochromism and concomitant fluorescence quenching, 1‐Ni displays slower photochromism but does not fluoresce, and 1‐Co and 2‐Co are neither photochromic nor fluorescent. It is shown here that the network entanglement dictates donor‐acceptor close contacts, which enable fluorescence originated from interligand charge transfer. The contacts also allow photoinduced electron transfer, which underlies photochromism and concomitant fluorescence response. The metal dependence in fluorescence and photochromism can be related to energy transfer through metal‐centered d‐d transitions. In addition, 1‐Cd is demonstrated to be a potential fluorescence sensor for sensitive and selective detection of UO22+ in water.
Organo‐originated and metal‐modulated photoresponsive properties were elucidated for a family of isostructural MOFs with tripyridinium‐tricarboxylate likers. Supramolecular entanglement between 2D networks dictates electron donor‐acceptor close contacts, which not only allow photoluminescence through interligand charge‐transfer excitation/emission but also cause photochromism through photoinduced electron transfer. Transition metal centers can weaken or prevent the photoresponsive properties because of energy transfer through d‐d transitions. The MOFs also show highly sensitive and selective fluorescence quenching response to UO22+ in water.
A two-dimensional Cd(ii) metal-organic framework (MOF) was constructed from a tris(pyridinium)-based hexacarboxylate zwitterionic ligand. The MOF shows a novel fashion of 2-fold 2D → 2D parallel ...entanglement. It is the entanglement that dictates close interlayer contacts between carboxylate (electron donor) and pyridinium (acceptor), which in turn impart the MOF with reversible photochromic properties through photoinduced electron transfer (PET). This is an extension of PET-based photochromism from bipyridinium to multipyridinium compounds. Thanks to the photoresponsive behaviour, the fluorescence of the MOF can be reversibly modulated or switched by photoirradiation. Besides, the fluorescence of the water-stable MOF in aqueous dispersion is very sensitive to nitrofuran antibiotics with high selectivity, and therefore the MOF is a good candidate of efficient and regenerable sensing material for determination of the antibiotics in water media.
Sensory materials that show color and/or fluorescence changes in response to specific gases or vapors have important applications in many fields. Here, we report the postsynthetic preparation of ...novel sensory metal–organic frameworks (MOFs) and their multiple responsive properties. Through postsynthetic N-amination, the 2,2′-bipyridyl spacers in a Zr(IV) MOF are partially transformed into N-aminobipyridinium. The new MOF (Zr-bpy-A) shows chromic behavior toward ammonia and amines because the electron-deficient pyridinium groups form charge-transfer complexes with amino moieties. It also shows a unique chromic response to formaldehyde owing to the Schiff-base condensation with the N-amino groups. Furthermore, the N-amino group can be used to graft different polycyclic aromatic hydrocarbons, which endow the MOF with strong fluorescence of variable colors and afford a high-contrast fluorescence response to ammonia/amines and formaldehyde associated with the chromic response. The presence of the unquaternized bipyridyl group also leads to a fluorescence response to HCl. The multiple responsive behaviors hold appeal for applications in sensing, switching, and antifake marking, which are illustrated with a test paper and writing ink.
A novel metal–organic framework (MOF), formulated as Cd2(TTVTC)Cl2(H2O)3·2H2O (1), was synthesized from a tetracarboxylate ligand (TTVTC2–) functionalized with the thiazolothiazole extended viologen ...(TTV2+) fluorophore. The MOF features three-dimensional (10,3)-d frameworks with 6-fold interpenetration. The MOF exhibits reversible photochromism, due to photoinduced electron transfer from carboxylate to TTV2+. The photoactivity benefits from the electron donor–acceptor contacts enabled by mutual interpenetration of the frameworks. This is the first demonstration of photochromism in TTV2+ derivatives. In addition, the fluorescence arising from the TTV2+ fluorophore can be reversibly modulated during the photochromic process. The work demonstrates the great potential of extended viologen based ligands in the construction of MOFs with dual photomodulable optical properties, which could find future applications in photoelectronics.
The exchangeable counterions in ionic metal–organic frameworks (IMOFs) provide facile and versatile handles to manipulate functions associated with the ionic guests themselves and host–guest ...interactions. However, anion-exchangeable stable IMOFs combining multiple anion-related functions are still undeveloped. In this work, a novel porous IMOF featuring unique self-penetration was constructed from an electron-deficient tris(pyridinium)-tricarboxylate zwitterionic ligand. The water-stable IMOF undergoes reversible and single-crystal-to-single-crystal anion exchange and shows selective and discriminative ionochromic behaviors toward electron-rich anions owing to donor–acceptor interactions. The IMOFs with different anions are good ionic conductors with low activation energy, the highest conductivity being observed with chloride. Furthermore, integrating Lewis acidic sites and nucleophilic guest anions in solid state, the IMOFs act as heterogeneous and recyclable catalysts to efficiently catalyze the cycloaddition of CO2 to epoxides without needing the use of halide cocatalysts. The catalytic activity is strongly dependent upon the guest anions, and the iodide shows the highest activity. The results demonstrate the great potential of developing IMOFs with various functions related to the guest ions included in the porous matrices.
This paper aims to develop a resonant accelerometer for high-sensitivity detection and to investigate the nonlinear vibration of the MEMS resonant accelerometer driven by electrostatic comb fingers. ...First, a nonlinear vibration model of the resonator with comb fingers in a MEMS resonant accelerometer is established. Then, the nonlinear and nonlinear stiffness coefficients are calculated and analyzed with the Galérkin principle. The linear natural frequency, tracking error, and nonlinear frequency offset are obtained by multi-scale method. Finally, to further analyze the nonlinear vibration, a sample-based stochastic model is established, and the uncertainty analysis method is applied. It is concluded from the results that nonlinear vibration can be reduced by reducing the resonant beam length and increasing the resonant beam width and thickness. In addition, the resonant beam length and thickness have more significant effects, while the resonant beam width and the single concentrated mass of comb fingers have little effect, which are verified by experiments. The results of this research have proved that uncertainty analysis is an effective approach in nonlinear vibration analysis and instructional in practical resonant accelerometer design.
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