A Redox-active Phenothiazine-based Pd2L4-type Coordination Cage and Its Isolable Crystalline Polyradical Cations.

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 14•+ through post-synthetic oxidation of a redox-active phenothiazine-based Pd2L4-type coordination cage 1. It's worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5-di-tert-butyl-4-methoxyphenyl substituent. The generation of 14•+ through reversible electrochemical oxidation is investigated by in situ UV-vis-NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 14•+ which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X-ray diffraction analysis of 14•+, whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 14•+. We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages.

Coordination cages integrated into swelling poly(ionic liquid)s for guest encapsulation and separation.

Coordination cages have been widely reported to bind a variety of guests, which are useful for chemical separation. Although the use of cages in the solid state benefits the recycling, the flexibility, dynamicity, and metal-ligand bond reversibility of solid-state cages are poor, preventing efficient guest encapsulation. Here we report a type of coordination cage-integrated solid materials that can be swelled into gel in water. The material is prepared through incorporation of an anionic FeII4L6 cage as the counterion of a cationic poly(ionic liquid) (MOC@PIL). The immobilized cages within MOC@PILs have been found to greatly affect the swelling ability of MOC@PILs and thus the mechanical properties. Importantly, upon swelling, the uptake of water provides an ideal microenvironment within the gels for the immobilized cages to dynamically move and flex that leads to excellent solution-level guest binding performances. This concept has enabled the use of MOC@PILs as efficient adsorbents for the removal of pollutants from water and for the purification of toluene and cyclohexane. Importantly, MOC@PILs can be regenerated through a deswelling strategy along with the recycling of the extracted guests.

P3MOT-decorated metal-porphyrin-based zirconium-MOF for the efficient electrochemical detection of 4-nitrobenzaldehyde.

A novel hybrid composite integrating conductive poly-3-methoxythiophene and PCN-222(Fe) (porphyrin-metal-organic frameworks) was synthesized using an in situ polymerization strategy. Leveraging the large specific area of MOFs and the low electrical resistance of conductive polymers, the modified electrode proved to be a promising candidate for the electrochemical detection of 4-nitrobenzaldehyde. The electrocatalytic response was measured using differential pulse voltammetry techniques and cyclic voltammetry, where the linear concentration range of analyte detection was estimated to be 0-900 µM and the detection limit was 0.233 µM with high selectivity toward the analyte. The sensor demonstrated repeatability and stability, allowing the direct electroanalytical measurement of 4-nitrobenzaldehyde in real samples with reliable recovery. This methodology expands the application of porphyrin MOFs for the electroanalytical sensing of environmental contaminants.

Confinement inside MOFs Enables Guest-Modulated Spin Crossover of Otherwise Low-Spin Coordination Cages.

Confinement of discrete coordination cages within nanoporous lattices is an intriguing strategy to gain unusual properties and functions. We demonstrate here that the confinement of coordination cages within metal-organic frameworks (MOFs) allows the spin state of the cages to be regulated through multilevel host-guest interactions. In particular, the confined in situ self-assembly of an anionic FeII4L6 nanocage within the mesoporous cationic framework of MIL-101 leads to the ionic MOF with an unusual hierarchical host-guest structure. While the nanocage in solution and in the solid state has been known to be invariantly diamagnetic with low-spin FeII, FeII4L6@MIL-101 exhibits spin-crossover (SCO) behavior in response to temperature and release/uptake of water guest within the MOF. The distinct color change concomitant with water-induced SCO enables the use of the material for highly selective colorimetric sensing of humidity. Moreover, the spin state and the SCO behavior can be modulated also by inclusion of a guest into the hydrophobic cavity of the confined cage. This is an essential demonstration of the phenomenon that the confinement within porous solids enables an SCO-inactive cage to show modulable SCO behaviors, opening perspectives for developing functional supramolecular materials through hierarchical host-guest structures.

Highly Efficient versus Null Electrochemical Enantioselective Recognition Controlled by Achiral Colinkers in Homochiral Metal-Organic Frameworks.

Chiral materials capable of electrochemical enantiomeric recognition are highly desirable for many applications, but it is still very challenging to achieve high recognition efficiency for lack of the knowledge of structure-property relationships. Here, we report the completely distinct enantiomeric recognition related to slightly different achiral colinkers in isomorphic homochiral metal-organic frameworks with the same chiral linker. Cu-TBPBe, for which the achiral colinker has two pyridyl rings connected by ─CH═CH─, shows excellent enantioselectivity and sensitivity for electrochemical recognition of l-tryptophan (Trp) with a detection limit of 3.16 nM. The l-to-d ratio of differential pulse voltammetric (DPV) currents reaches 53, which is much higher than the values (2-14) reported for previous electrochemical sensors. By contrast, Cu-TBPBa, in which the achiral colinker has -CH2-CH2- between pyridyl rings, is incapable of discrimination between l-Trp and d-Trp. Structural and spectral analyses suggest that the achiral conjugated colinker and the chiral moieties around it cooperate to produce a chiral pocket in favor of enantioselective adsorption through multiple hydrogen-bonding and π-π stacking interactions. The work demonstrated that Cu-TBPBe can be used to fabricate reliable electrochemical sensors for ultrasensitive quantification of Trp enantiomers in racemic mixtures and in complex biological systems such as urine. The work also highlights that an achiral coligand can be of vital importance in determining enantiomeric discrimination, opening up a new avenue for the design of chiral sensing materials.

Guanidine-Based Covalent Organic Frameworks: Cooperation between Cores and Linkers for Chromic Sensing and Efficient CO2 Conversion.

C(sp)-H carboxylation with CO2 is an attractive route of CO2 utilization and is traditionally promoted by transition metal catalysts, and organocatalysis for the conversion remains rarely explored and challenging. In this article, triaminoguanidine-derived covalent organic frameworks (COFs) were used as platforms to develop heterogeneous organocatalysts for the reaction. We demonstrated that the COFs with guanidine cores and pyrazine linkers show high catalytic performance as a result of the cooperation between cores and linkers. The core is vitally important, which is deprotonated to the guanidinato group that binds and activates CO2. The pyrazine linker collaborates with the core to activate the C(sp)-H bond through hydrogen bonding. In addition, the COFs show acid- and base-responsive chromic behaviors thanks to the amphoteric nature of the core and the auxochromic effect of the pyrazine linker. The work opens up new avenues to organocatalysts for C-H carboxylation and chromic materials for sensing and switching applications.

A Cu-functionalized MOF and multi-walled carbon nanotube composite modified electrode for the simultaneous determination of hydroquinone and catechol.

Designing MOF-based materials with desired electrochemical activity and high electron conductivity may yield a novel electrochemical sensor that effectively detects various organic pollutants and conducts health monitoring. This study developed a facile and versatile electrochemical sensor for simultaneously monitoring the environmental pollutants hydroquinone (HQ) and catechol (CT). The electrodes are fabricated by modifying a GCE with a Cu-functionalized MOF (UiO-bpydc-Cu) and multi-walled carbon nanotubes (MWCNTs). The Cu-functionalized MOF effectively improved the electronic conductivity by metalating the 2,2'-bipyridyl-derived UiO-bpydc with Cu2+ ions. Moreover, due to the synergic effect, the composite electrode exhibits a significant voltammetric response to HQ's and CT's electro-redox. A rapid and sensitive method of synchronously detecting HQ and CT has been established by differential pulse voltammetry (DPV). The experiments reveal that the linear response ranges were 0.5-565 µM and 1-1350 µM for HQ and CT, respectively, with low detection limits of 0.361 µM and 0.245 µM. The proposed UiO-bpydc-Cu/MWCNTs/GCE electrochemical sensor shows high sensitivity, good anti-interference, reproducibility, and stability. It can also be applied for detecting HQ and CT in actual samples.

Two cationic iron-based crystalline porous materials for encapsulation and sustained release of 5-fluorouracil.

Iron-based crystalline porous materials (CPMs) emerged as a new class of biodegradable and non-toxic materials of high interest for drug delivery systems (DDSs) due to their high loading capacity and controllable structures. This work constructed two kinds of Fe-CPM coordination polymers (CPM-83 and CPM-85) from typical oxo-centered trimers of the iron octahedra cluster [Fe3O(RCOO)3(TPT)] with two functional modules. The tri-topic pyridine ligand (TPT) occupied the open metal sites of the trinuclear cluster, precluding the attachment of neutralizing anions, leading to three-dimensional frameworks with a positive charge and higher stability. Moreover, the triazine ligand TPT divides the original columnar channel into small domains, improving the adsorption efficiency and maximizing the host-guest interaction. Hence, the suitable pore size and electrostatic force make the materials highly adsorption selective for the anticancer drug 5-fluorouracil (5-Fu). We show that Fe-CPM-83 and Fe-CPM-85 loaded with 5-Fu are efficient drug delivery vehicles with loading content as high as 60.5 (wt%) and 32.8 (wt%) within 2-5 h of loading time. Simultaneously, their sustained release kinetics can be up to 96 hours with a completely different pH-responsive controlled release. The released content is 77% or 85% for each complex, significantly prolonging the release process and decreasing the plasma concentration. The MTT assay was performed on mouse fibroblasts (L929) to demonstrate the satisfactory biocompatibility of the matrix. This work has momentous research significance and application value for developing novel drug-delivery materials.

Anion-Afforded Functions of Ionic Metal-Organic Frameworks: Ionochromism, Anion Conduction, and Catalysis.

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.

Metal-Organic Frameworks with Novel Catenane-like Interlocking: Metal-Determined Photoresponse and Uranyl Sensing.

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 UO2 2+ in water.

Dual functions of pH-sensitive cation Zr-MOF for 5-Fu: large drug-loading capacity and high-sensitivity fluorescence detection.

Nanomaterials, as carriers of small molecular drugs, have been a focal point in recent years. In this work, a carbazolyl functionalized metal-organic framework, UiO-67-CDC, was successfully synthesized employing the ligand 9H-carbazole-2,7-dicarboxylic acid (9H-2,7-CDC). Postsynthetic approaches targeted the cationization and replacement of the Lewis base carbazole site with two methyl groups, resulting in the positively charged skeleton, which has proven to be a promising carrier for the anticancer drug 5-fluorouracil (5-Fu). The prepared cationic framework UiO-67-CDC-(CH3)2 showed moderately high surface area, hierarchical pore structures, and positive surface characteristics, which effectively and selectivity encapsulated the electron-rich 5-Fu molecules through electrostatic attraction, with a relatively high loading of up to 56.5% (wt%). The drug delivery in simulated blood environment (pH = 7.4) exhibited a more effective release, demonstrating a physiological pH-responsive sustained release. Significantly, the electron-deficient Zr-MOF itself, as a kind of high-sensitivity fluorescence detector, has a unique fluorescence "turn-on" effect with 5-Fu. These results pave the way towards designing surface-engineered MOF materials of interest in drug delivery and fluorescent sensing applications.

Positive Cooperative Protonation of a Metal-Organic Framework: pH-Responsive Fluorescence and Proton Conduction.

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.

Synthesis and Acid-Responsive Properties of a Highly Porous Vinylene-Linked Covalent Organic Framework.

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.

Chromic and Fluorescence-Responsive Metal-Organic Frameworks Afforded by N-Amination Modification.

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.

An in situ approach to functionalize metal-organic frameworks with tertiary aliphatic amino groups.

Metal-catalyzed reductive amination of formyl-containing linkers with N,N-dialkylformamide solvents is concomitant with the solvothermal coordination assembly, leading to novel MOFs functionalized with tertiary aliphatic amino groups. This illustrates a novel one-pot strategy to functionalize MOFs through in situ organic transformation. The UiO-66 MOFs partially functionalized with the amino groups are highly active heterogeneous catalysts for Knoevenagel condensation.

A pH-Sensing Fluorescent Metal-Organic Framework: pH-Triggered Fluorescence Transition and Detection of Mycotoxin.

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.

Effects of Different Counter Anions on Solid-State Electron Transfer in Viologen Compounds: Modulation of Color and Piezo- and Photochromic Properties.

Charge transfer (CT) and electron transfer (ET) underlie the various applications of viologen compounds. However, the CT and ET in solids are still insufficiently understood and difficult to control, which is challenging but fundamental to the design of multifunctional materials. Our strategy is to attempt a delicate control of CT and ET by subjecting model compounds to pressure. In this work, a series of viologens of the same cation with different anions show anion-dependent color and piezo-/photochromism due to ground-state CT and stimuli-induced ET; the ease of solid-state ET can be tuned in the order of Cl- > Br- > I-/BF4-/PF6-/ClO4-. With in situ high pressure UV-vis experiments, we also observed unexpectedly the pressure-induced solid-state ET in [H2bcpV]·I2 besides the pressure modulation of the CT absorption. It proves pressure is a more powerful stimulus than light in tuning solid-state CT and ET.

Distinct and Selective Amine- and Anion-Responsive Behaviors of an Electron-Deficient and Anion-Exchangeable Metal-Organic Framework.

Smart materials that respond to chemical stimuli with color or luminescence changes are highly desirable for daily-life and high-tech applications. Here, we report a novel porous metal-organic framework (MOF) that shows multiple, selective, and discriminative responsive properties owing to the combination of different functional ingredients [tripyridinium chromogen, Eu(III) luminophore, cationic framework, and special porous structure]. The MOF contains two interpenetrated three-dimensional cationic coordination networks built of a tetrahedral [Eu4(µ3-OH)4] cluster and a tripyridinium-tricarboxylate zwitterionic linker. It shows reversible and discriminative chromic response to aliphatic amines and aniline through different host-guest interactions between electron-deficient pyridinium and electron-rich amines. The size- and shape-selective response to aliphatic amines is ascribed to the radical formation through host-guest electron transfer, whereas the response to aniline is ascribed to the formation of sandwich-type acceptor-donor-acceptor complexes. The MOF is capable of reversible anion exchange with various anions and shows selective and discriminative ionochromic response to iodide, bromide, and thiocyanate, which is attributed to charge-transfer complexation. The above chromic behaviors are accompanied by efficient quenching of Eu(III) photoluminescence. The MOF represents a multi-stimuli dual-output responsive system. It can be used for discrimination and identification of anions and amines. The potential use in invisible printing, reusable sensory films, and optical switches was demonstrated by the ink and the membrane made of the MOF and organic polymers.

Photoresponsivity and antibiotic sensing properties of an entangled tris(pyridinium)-based metal-organic framework.

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.

Selective chemochromic and chemically-induced photochromic response of a metal-organic framework.

The Zn(ii) MOF with a tripyridinium-based hexacarboxylate shows direct color change on exposure to small primary amines and UV-assisted color response on exposure to small alcohols. The reversible, group-specific and size-selective chemochromic/chemophotochromic behaviours are ascribed to spontaneous/photoinduced guest-to-host electron transfer within the unique confined space furnished with electron-deficient sites.