A fluorescent MOF and its synthesized MOF@cotton composite: Ratiometric sensing of vitamin B2 and antibiotic drug molecule.

Here, we demonstrated the synthesis of a zinc based luminescent MOF, 1 (NDC = 2,6- naphthalenedicarboxylate) for the ratiometric detection of biomarker riboflavin (RBF; vitamin B2) in water dispersed medium. Further, this MOF detected two other antibiotic drug molecules, nitrofurantoin (NFT) and nitrofurazone (NZF). The detection of these analytes is very quick (∼seconds), and the limit of detection (LOD) for RBF, NZF and NFT are calculated as 16.58 ppm, 47.63 ppb and 56.96 ppb, respectively. The detection of these analytes was also comprehended by solid, solution, cost-effective paper strip method i.e., triphasic identification capabilities. The sensor is reusable without losing its detection efficacy. The sensor further showed the recognition abilities of these antibiotics in real field samples (river water, urine and tablet) and RBF in vitamin B2 pills and food samples (milk and cold drinks). The sensing merit of 1 urged us to fabricate of 1@cotton fabric composite, which exhibited the colorimetric detection of these analytes. In-depth experimental analysis suggested that the occurrence of photo-induced electron transfer (PET), fluorescence resonance energy transfer (FRET), and the inner filter effect (IFE) are the possible sensing mechanisms for the recognition of the antibiotics drug. The FRET mechanism is responsible for the recognition of RBF. The sensing mechanism is further supported by the theoretical analysis and the excited lifetime measurement.

Fluorescent MOF and Its Gel Composite for the Fluorescence Recovery "Turn-On" Detection of Al3+ Ions and "Turn-Off" Detection of Oxo-Anions.

The exploration of smart sensors is of great significance for the selectivity, sensitivity, and ability to show the low detection limit for the target analyte. Here, we have used the linker H2L (5-((anthracen-9-ylmethyl)amino)isophthalic acid) for the construction of {[Cd(L)(DMF)(H2O)2]·H2O}n (1) which is in order with the chromophore anthracene moiety and the free -NH functionality as a guest interaction site. This framework showed the luminescence recovery "turn-on" detection of the Al3+ ion in an aqueous solution. An exhaustive mechanism study disclosed that the Lewis acid-base-type interaction between the Al3+ ion and the -NH functionality of the linker in the framework revealed that the absorbance caused an enhancement for the "turn-on" sensing event. Besides the "turn-on" sensing event, the "turn-off" sensing phenomenon of 1 is also noticed when it detects the hazardous oxo-anions (MnO4- and CrO42-) with limit of detection values of 17.08 and 19.91 ppb, respectively. The detection of these diverse analytes are very fast (10 s) and they can also be recognized through a colorimetric response. The sensing mechanisms for these analytes are established by photoinduced electron transfer, Forster resonance energy transfer, and inert filter effect along with theoretical investigation. Furthermore, to show the sensing application of 1 in a versatile podium, a MOF gel composite, 1@AA (AA = Agar-Agar), was developed from 1 with AA. Interestingly, 1@AA showed the colorimetric detection of these analytes under UV light. Therefore, sensor 1 behaves as a smart sensory material for the recognition of the above analytes through a simultaneous "turn-on" and "turn-off" effect.

Sensing of hyperprolinemia biomarker and its recognition in biological sample through "turn-on" event by Zn-based metal-organic framework.

A hydrogen bonded ability metal organic framework (MOF, 1Zn) is used for the ultra-sensitive "turn-on" detection of hyperprolinemia biomarker with ultrafast (within 5 s) colorimetric response making the first MOF based hyperprolinemia biomarker sensor. The detection limit (4.46 ppb) is outperformed compared to all contemporary hyperprolinemia biomarker based sensors. Further, the sensor showed the recognition of biomarker in biological sample (human saliva). The detection of biomarker is also realized through colorimetric response (solution based and paper strip method). The mechanism of sensing is established through the electron transfer and the absorption caused emission (ACE). Moreover, the theoretical study is performed to support the sensing mechanism. The control titration of 1Zn suggest that the free -NH2 group of linker in 1Zn is involved in supramolecular interaction (hydrogen bonding) with the carboxylic group present on biomarker results the facile occurrence of electron transfer and ACE. Consequently, the luminescence "turn-on" effect of 1Zn for hyperprolinemia biomarker is observed.

Engineering of metal-organic frameworks (MOFs) for thermometry.

Metal-organic frameworks (MOFs ) are excellent candidates for use in chemistry, material sciences and engineering thanks to their interesting qualitative features and potential applications. Quite interestingly, the luminescence of MOFs can be engineered by regulation of the ligand design, metal ion selection and encapsulation of guest molecules within the MOF cavity. Temperature is a very crucial physical parameter and the market share of temperature sensors is rapidly expanding with technology and medicinal advancement. Among the wide variety of available temperature sensors, recently MOFs have emerged as potential temperature sensors with the capacity to precisely measure the temperature. Lanthanide-based thermometry has advantages because of its ratiometric response ability, high quantum yield and photostability, and therefore lanthanide-based MOFs were initially focused on to construct MOF thermometers. As science and technology have gradually changed, it has been observed that with the inclusion of dye, quantum dots, etc. within the MOF cavity, it is possible to develop MOF-based thermometry. This review consolidates the recent advances of MOF-based ratiometric thermometers and their mechanism of energy transfer for determining the temperature (thermal sensitivity and temperature uncertainty). In addition, some fundamental points are also discussed, such as concepts for guiding the design of MOF ratiometric thermometers, thermometric performance and tuning the properties of MOF thermometers.

A Zn(II) coordination polymer as a dual sensor for ppb level detection of antibiotics and organo-toxins in a green solvent.

Herein, we describe the synthesis of a new fluorescent d10 coordination polymer, [Zn2(CFDA)2(BPEP)]n·nDMF (CP-1) under solvothermal reaction condition using zinc metal ion. In CP-1, Zn(II) ion along with CFDA and BPED ligand forms a 2-fold self-interpenetrated 3D coordination polymers. This CP-1 is characterized by the single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), infrared spectra, optical microscope image and thermogravimetric analysis and the framework is found to maintain its structural stability in different solvents. The framework (CP-1) detected antibiotics (NFT (nitrofurantoin) and NZF (nitrofurazone)) and organo-toxin trinitrophenol in aqueous dispersed medium. Apart from the fast responsive (10 s), the detection limit for them was found at ppb level. The detection of these organo-aromatics were also comprehended by the colorimetric response through solid, solution and low cost paper strip technique i.e., triple mode recognition capability. The probe is re-usable without changing in its sensing efficiency and in addition, it has been applied for the detection of these analytes in the real field specimens (soil, river water, human urine and commercial tablet). The sensing ability is established by in-depth experimental analysis and the life time measurement where mechanism such as photo induced electron transfer (PET), fluorescence resonance energy transfer (FRET), inner filter effect (IFE) was recognized. The presence of guest interaction sites on the linker backbone in CP-1 induces diverse supramolecular interaction with the targeted analytes results to bring them in proximity for the occurrence of these sensing mechanism. The Stern-Volmer quenching constant values of CP-1 for the targeted analytes are admirable and the low detection limit (LOD) values for NFT, NZF and TNP are found to be 34.54, 67.79 and 43.93 ppb respectively. Further, the DFT theory is carried out in details to justify the sensing mechanism.

Highly Luminescent MOF and Its In Situ Fabricated Sustainable Corn Starch Gel Composite as a Fluoro-Switchable Reversible Sensor Triggered by Antibiotics and Oxo-Anions.

Frequent use of antibiotics and the growth of industry lead to the pollution of several natural resources which is one of the major consequences for fatality to human health. Exploration of smart sensing materials is highly anticipated for ultrasensitive detection of those hazardous organics. The robust porous hydrogen bonded network encompassing a free-NH2 moiety, Zn(II)-based metal-organic framework (MOF) (1), is used for the selective detection of antibiotics and toxic oxo-anions at the ppb level. The framework is able to detect the electronically dissimilar antibiotic sulfadiazine and nitrofurazone via fluorescence "turn-on" and "turn-off" processes, respectively. The antibiotic-triggered reversible fluoro-switching phenomena (fluorescence "on-off-on") are also observed by using the fluorimetric method. An extensive theoretical investigation was performed to establish the fluoro-switching response of 1, triggered by a class of antibiotics and also the sensing of oxo-anions. This investigation reveals that the interchange of the HOMO-LUMO energy levels of fluorophore and analytes is responsible for such a fluoro-switchable sensing activity. Sensor 1 showed the versatile detection ability which is reflected by the detection of a carcinogenic nitro-group-containing drug "roxarsone". In view of the sustainable environment along with quick-responsive merit of 1, an in situ MOF gel composite (1@CS; CS = corn starch) is prepared using 1 and CS due to its useful potential features such as biocompatibility, toxicologically innocuous, good flexibility, and low commercial price. The MOF composite exhibited visual detection of the above analytes as well as antibiotic-triggered reversible fluoro-switchable colorimetric "on-off-on" response. Therefore, 1@CS represents a promising smart sensing material for monitoring of the antibiotics and oxo-anions, particularly appropriate for the real-field analysis of carcinogenic drug molecule "roxarsone" in food specimens.

Highly regenerative, fast colorimetric response for organo-toxin and oxo-anions in an aqueous medium using a discrete luminescent Cd(II) complex in a heterogeneous manner with theoretical revelation.

The highly luminescent complex [CdQ2(H2O)2] (1) shows ultra-selectivity and high sensitivity to the explosive organo-toxin trinitrophenol (TNP). This detection is extremely fast with a high quenching constant (5.3 × 104 M-1) and a very low limit of detection (LOD) of 137 nM/59 ppb. This motivated us to detect the lethal carcinogenic arsenical drug roxarsone (ROX), which is reported here for the first time. The quenching constant and LOD for ROX using 1 were found to be 4.9 × 104 M-1 and 86 nM (or 37 ppb), respectively. Moreover, the probe also recognizes three lethal toxic oxo-anions (MnO4-, Cr2O72- and CrO42-) with outstanding quenching constant (2.2 × 104 M-1, 1.4 × 104 M-1 and 1.1 × 104 M-1) and very low LODs (141 nM/61 ppb, 178 nM/78 ppb and 219 nM/95 ppb). Compared to the previously reported homogeneous sensing nature of the discrete complexes, our complex showed the detection of toxic pollutants in a heterogeneous manner, which results in high recyclability and hence multi-cycle sensing capability. Interestingly, 1 shows the possibility for real-time monitoring through naked eye detection by visible colorimetric changes in solid, solution and strip paper methods, i.e., triphasic detection ability. In addition, the sensor also exhibited the cross-sensing ability for these pollutants. The experimental sensing mechanism is strongly supported by the exhaustive theoretical investigation. Based on the fluorescence signal shown by each analyte, an integrated AND-OR logic gate is constructed. Furthermore, the sensing ability of 1 remains intact towards the detection of versatile real field samples including lethal carcinogenic arsenical drug roxarsone in the real food sample.

Significance of an Environmental Gas Cell to Obtain a Fully Dehydrated Form and CO2-Pressurized Structure of a Metal-Organic Framework Using In Situ Single-Crystal X-ray Diffraction at 298 K.

The single-crystal X-ray diffraction method was employed to characterize a rigid hydrated metal-organic framework (MOF), [Co2(MA)(INA)·2H2O]n, that displays an affinity toward water molecules under ambient conditions after dehydration. The fully dehydrated form was obtained using an environmental gas cell technique in a stepwise manner followed by its CO2-pressurized structure at 298 K using in situ crystallography.

Amine-substituent induced highly selective and rapid "turn-on" detection of carcinogenic 1,4-dioxane from purely aqueous and vapour phase with novel post-synthetically modified d10-MOFs.

Herein, an amine decorated Cd(II) metal-organic framework (MOF) with a uninodal 6-c topology was synthesized as a suitable platform for facile post-synthetic modification (PSM). The as-synthesized parent d10-MOF (1) with free -NH2 centers, when functionalized with two different carbonyl substituents (1-naphthaldehyde and benzophenone) of varying conjugation, produces two novel luminescent MOFs (LMOFs) viz.PSM-1 and PSM-2. The judicious incorporation of carbonyl substituents into the skeleton of 1 was rationalized via ESI-MS, 1H-NMR, FT-IR and PXRD analyses. Interestingly, both PSM-1 and PSM-2 show 'turn-on' luminescent behaviour in the presence of 1,4-dioxane with the limit of detection (LOD) as 1.079 ppm and 2.487 ppm, respectively, with prompt response time (∼55 s & ∼58 s, respectively). The inhibition of PET is comprehended to be the prime reason for luminescence enhancement upon interaction with the targeted analyte which was further validated from DFT calculations. In continuation, the PSM-MOFs were equally responsive towards 1,4-dioxane in several complex environmental matrices and cosmetic products. Additionally, vapor phase detection of 1,4-dioxane using PSM-MOFs has also been demonstrated as an additional advantage ensuring propagation of future research endeavour.

Solvothermal Synthesis of High-Performance d10-MOFs with Hydrogel Membranes @ "Turn-On" Monitoring of Formaldehyde in Solution and Vapor Phase.

Herein, two luminescent porous networks (CMERI-1 & CMERI-2) have been reported for the efficient detection of formaldehyde (FA) from aqueous medium. Judicious solvent screening using a high-throughput solvothermal procedure leads to two completely different metal-organic framework (MOFs) with different architectures. It is perceived that the framework CMERI-1 shows better sensitivity with a very short response time (1 min) in the realm of FA detection due to the facile imine (-N═CH-) formation, which is restricted in the case of CMERI-2. The fluorescence "turn-on" behavior is ascribed due to the inhibition of photoinduced electron transfer (PET) (from amine subunit to secondary building unit) process. The detection limits of CMERI-1 & CMERI-2 toward FA in aqueous medium were found to be 0.62 µM (0.019 ppm) and 1.39 µM (0.041 ppm), respectively, that lie far below the intracellular concentration of formaldehyde (100-400 µM). In addition, MOF-based hydrogel membrane was fabricated, which shows vapor-phase detection of FA, which is hitherto unexplored in this realm. Moreover, the response mechanisms of MOFs are supported by density functional theory (DFT) and Fukui indices analysis. The high stability of the porous frameworks along with its interesting sensing features such as fast recognition phenomenon, appreciable detection limit, etc. instigated us to explore its real-world applicability in various food sample and water analyses. In view of the modular design principle of our polymeric probe, the proposed approach could open a new horizon to construct powerful sensing materials for the ultrafast detection of other industrial pollutants in the domain of supramolecular and analytical chemistry.

Stimuli -triggered fluoro-switching in metal-organic frameworks: applications and outlook.

The design and synthesis of efficient sensor materials with fast-responsive and ultrasensitive detection ability is critical to monitor ecological safety, supervise human health, control industrial wastes, and govern food quality among others. Metal-organic frameworks (MOFs) or coordination polymers (CPs) are a new class of porous crystalline materials that have emerged in several potential applications in last two decades. In particular, applications of MOFs as sensory scaffolds for the detection of hazardous pollutants have attracted researchers due to their fabulous structural characteristics and wide range of pore environment tunability. Among several transducer procedures, the luminescence detection of a particular analyte is immensely desirable as it is easy to handle and cost effective, where visual changes in physicochemical attributes can be comprehended via a quick naked eye detection. The porous nature of MOFs facilitates the pre-concentration of target analytes within the pore structure and provides superior host-guest interaction with good detection limits when compared to conventional materials. To this end, guest-induced fluorescence switching in sensory MOFs with good recyclability and unique detectable fingerprints are of particular importance to benefit futuristic monitoring aptitudes and promises environmental remediation. In this review, we present the latest literature based on the analyte-responsive modulation of fluorescence intensity in MOFs towards the detection of target pollutants and discuss the underlying sensing mechanism, which can assist in developing new useful nano-scale devices and sensors.

Porosity Switching in Polymorphic Porous Organic Cages with Exceptional Chemical Stability.

Porous solids that can be switched between different forms with distinct physical properties are appealing candidates for separation, catalysis, and host-guest chemistry. In this regard, porous organic cages (POCs) are of profound interest because of their solution-state accessibility. However, the application of POCs is limited by poor chemical stability. Synthesis of an exceptionally stable imine-linked (4+6) porous organic cage (TpOMe-CDA) is reported using 2,4,6-trimethoxy-1,3,5-triformyl benzene (TpOMe) as a precursor aldehyde. Introduction of the -OMe functional group to the aldehyde creates significant steric and hydrophobic characteristics in the environment around the imine bonds that protects the cage molecules from hydrolysis in the presence of acids or bases. The electronic effect of the -OMe group also plays an important role in enhancing the stability of the reported POCs. As a consequence, TpOMe-CDA reveals exceptional chemical stability in neutral, acidic and basic conditions, even in 12 m NaOH. Interestingly, TpOMe-CDA exists in three different porous and non-porous polymorphic forms (α, ß, and γ) with respect to differences in crystallographic packing and the orientation of the flexible methoxy groups. All of the polymorphs retain their crystallinity even after treatment with acids and bases. All the polymorphs of TpOMe-CDA differ significantly in their properties as well as morphology and could be reversibly switched in the presence of an external stimulus.

A porous two-dimensional Zn(ii)-coordination polymer exhibiting SC-SC transmetalation with Cu(ii): efficient heterogeneous catalysis for the Henry reaction and detection of nitro explosives.

The linker 5-(benzylamino)isophthalic acid (H2L) forms a robust 2D Zn(ii)-coordination polymer, {[Zn8(L)6(µ3-OH)4(H2O)6]·(DMF)·(H2O)2.5}n(1Zn) consisting of [Zn4(µ3-OH)2]6+ SBUs. It further shows strong ππ interactions between the layers to form an overall 3D structure with well-defined channels. Metal bound water molecules are directed towards these channels. Upon heating, these metal bound water molecules are lost along with lattice solvent molecules to afford coordinatively unsaturated metal centers that can be utilized as an efficient heterogeneous catalyst for the C-C bond forming nitroaldol or Henry reaction. The solid catalyst can be recycled at least three times without losing its catalytic activity. The easily accessible channels in 1Zn are found suitable for the SC-SC transmetalation reaction with Cu(ii) producing 1Cu. The catalytic activity of 1Cu is found to be comparable to that of 1Zn. Furthermore, the framework 1Zn gives high emission in DMSO, which can be efficiently quenched by trace amounts of nitro explosives. All the complexes have been characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR, thermogravimetry and elemental analysis.

Development and Validation of an LC-MS/MS-ESI Method for Comparative Pharmacokinetic Study of Ciprofloxacin in Healthy Male Subjects.

A sensitive, specific and reproducible liquid chromatography coupled to tandem mass spectrometric method was developed and validated for the estimation of ciprofloxacin, an extensively used second-generation quinolone antibiotics, in human plasma. A liquid-liquid extraction of ciprofloxacin and the internal standard, ofloxacin, has been approached from the biological matrix using chloroform. Chromatographic separation was achieved in positive ion modes, isocratically on a 3.5 µm C18 analytical column (75 mm×4.6 mm, i.d.) with 0.2% formic acid solution in water: methanol (10:90, v/v) as mobile phase, at a flow rate of 0.5 mL.min-1. The MS/MS ion transitions were monitored as 332.0→231.3 for ciprofloxacin and 362.2→261.0 for IS. The method showed good linearity in the range of 0.01-5.00 µg.mL-1 (r2 >0.99) with a good precision (3.37-12.60%) and accuracy (87.25-114%). At the same time, ciprofloxacin was found to be stable during stability studies viz. bench-top, auto-sampler, freeze-thaw cycle and long-term. The developed and validated method was successfully applied to measure plasma ciprofloxacin concentrations in a single dose bioequivalence study.

A Partially Fluorinated, Water-Stable Cu(II)-MOF Derived via Transmetalation: Significant Gas Adsorption with High CO2 Selectivity and Catalysis of Biginelli Reactions.

A partially fluorinated, angular tetracarboxylic acid linker (H4L) incorporating a pendant amine moiety forms a three-dimensional Zn(II) framework, 1. The structure consists of paddle-wheel Zn2(CO2)4 secondary building units (SBUs) and Zn12(CO2)24 supramolecular building blocks (SBBs). Thermal stability of 1 is found to be low. However, it undergoes transmetalation reaction with Cu(II) at room temperature without losing crystallinity affording an isostructural framework, 1Cu. Framework 1Cu is thermally robust and allows generation of the solvent-free porous framework 1Cu' upon activation with coordinatively unsaturated metal centers. Framework 1Cu' exhibits water stability and at 77 K, adsorbs 2.56 wt % of H2 up to 1 bar that significantly increases to 4.01 wt % at 13 bar. Also, this framework gives a high adsorption of 164.70 cc/g of CH4 (11.7 wt %) at 303 K and 60 bar. The channel surfaces decorated with -NH2 group and unsaturated metal centers in 1Cu' allow a promising 36.4 wt % of CO2 adsorption at 1 bar and 273 K. Moreover, it exhibits pronounced selectivity of CO2 adsorption over N2 and H2 at 273 K. Finally, the versatility of 1Cu' is shown by its excellent heterogeneous catalytic activity in the Biginelli coupling reactions involving an aldehyde, urea, and ethylacetoacetate to afford dihydroprimidinones.

A Porous Cu(II)-MOF with Proline Embellished Cavity: Cooperative Catalysis for the Baylis-Hillman Reaction.

l-Proline has been covalently attached in a rigid linear ligand, H4L, having an isophthalate moiety at each terminal to form the chiral ligand, H4LPRO. This linker has been used for the construction of a porous MOF, LCuPRO. The free l-proline moiety in the cavity of the framework in the presence of imidazole as a cocatalyst functions synergistically to catalyze the Baylis-Hillman reaction between α,ß-unsaturated carbonyl compounds and aromatic aldehydes. High porosity of the framework is proven by the nitrogen adsorption isotherm.

Linker-Induced Structural Diversity and Photophysical Property of MOFs for Selective and Sensitive Detection of Nitroaromatics.

The linker [1,1':3',1″-terphenyl]-4,4',4″,6'-tetracarboxylic acid (H4L) was used to construct two three-dimensional (3D) metal-organic frameworks (MOFs), namely, {[Cd2(L)(L1)(DMF)(H2O)](2DMF)(3H2O)}n (1) and {[Cd4(L)2(L2)3(H2O)2](8DMF)(8H2O)}n (2) (DMF = N,N'-dimethylformamide) in the presence of colinkers 4,4'-bipyridine (L1) and 2-amino-4,4'-bipyridine (L2), respectively, under solvothermal condition. A small change in the colinker leads to significant differences in the overall structure of the MOFs. Topological analysis reveals that the framework 1 exhibits 6,4-connected forbidden sub-configuration (FSC) topology, while the framework 2 exhibits twofold interpenetrated and (3,4,4)-connected new network topology with Schläfli point symbol {4.6(2)}{4.6(4).8}{4(2).6(2).8(2)}. The crystallographic investigation reveals the framework 2 having single helix structure, which is further coiled through noncovalent interaction, afforded a double-helix structure similar to DNA. These double helices are further connected through the colinker L2 to form an overall 3D structure. Besides framework 2 exhibits remarkable fluorescence intensity compared to 1. Framework 2 displayed a strong emission at 457 nm when a sample of 2 was dispersed in ethanol and excited at 334 nm. This emission is selectively and completely quenched in the presence of 2,4,6-trinitrophenol (TNP) allowing its detection in the presence of other nitroaromatic compounds. The quenching constant for TNP was found to be 3.89 × 10(4) M(-1), which is 26 times higher than that of TNT demonstrating greater and selective quenching ability. The emission is restored to its original value when the sample after collected by filtration is dispersed in fresh ethanol for 1 d. Interestingly, when solid 2 is exposed to different nitroaromatic compounds, its emission is quenched selectively in the presence of nitrobenzene. In this case, the emission is restored upon heating the sample to 150 °C for 2 h.

A Versatile CuII Metal-Organic Framework Exhibiting High Gas Storage Capacity with Selectivity for CO2 : Conversion of CO2 to Cyclic Carbonate and Other Catalytic Abilities.

A linear tetracarboxylic acid ligand, H4 L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) LM (M=ZnII , CuII ). Framework LCu can also be obtained from LZn by post- synthetic metathesis without losing crystallinity. Compared with LZn , the LCu framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, LCu '. At 77 K, LCu ' absorbs 2.57 wt % of H2 at 1 bar, which increases significantly to 4.67 wt % at 36 bar. The framework absorbs substantially high amounts of methane (238.38 cm3 g-1 , 17.03 wt %) at 303 K and 60 bar. The CH4 absorption at 303 K gives a total volumetric capacity of 166 cm3 (STP) cm-3 at 35 bar (223.25 cm3 g-1 , 15.95 wt %). Interestingly, the NH2 groups in the linker, which decorate the channel surface, allow a remarkable 39.0 wt % of CO2 to be absorbed at 1 bar and 273 K, which comes within the dominion of the most famous MOFs for CO2 absorption. Also, LCu ' shows pronounced selectivity for CO2 absorption over CH4 , N2 , and H2 at 273 K. The absorbed CO2 can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20 bar, 120 °C). Finally, LCu ' is found to be an excellent heterogeneous catalyst in regioselective 1,3-dipolar cycloaddition reactions ("click" reactions) and provides an efficient, economic route for the one-pot synthesis of structurally divergent propargylamines through three-component coupling of alkynes, amines, and aldehydes.

Significant Gas Adsorption and Catalytic Performance by a Robust Cu(II) -MOF Derived through Single-Crystal to Single-Crystal Transmetalation of a Thermally Less-Stable Zn(II) -MOF.

By using a bent tetracarboxylic acid ligand that incorporates a pendent-NH2 functional group, a 3D Zn(II)-framework (1) based on Zn2 (CO2)4 secondary building units and Zn12 (CO2)24 supramolecular building blocks has been synthesized. Framework 1 is thermally less stable, which precludes its application as a porous framework for gas adsorption or catalytic studies. This framework undergoes single-crystal to single-crystal transmetalation to give isostructural 1Cu. Unlike 1, the Cu(II) analogue is very stable and can be activated by removing metal-bound lattice solvent molecules by heating to afford 1Cu'. The activated 1Cu' exhibits excellent H2 storage (2.29 wt%) at 77 K and a high 32.1 wt% CO2 uptake at 273 K. Additionally, it displays significant selectivity for CO2 adsorption over N2 and H2 and can catalyse size-selective Knoevenagel condensation reactions.

Versatile Tailoring of Paddle-Wheel Zn(II) Metal-Organic Frameworks through Single-Crystal-to-Single-Crystal Transformations.

A new tetracarboxylate ligand having short and long arms formed 2D layer Zn(II) coordination polymer 1 with paddle-wheel secondary building units under solvothermal conditions. The framework undergoes solvent-specific single crystal-to-single crystal (SC-SC) transmetalation to produce 1Cu . With a sterically encumbered dipyridyl linker, the same ligand forms non-interpenetrated, 3D, pillared-layer Zn(II) metal-organic framework (MOF) 2, which takes part in SC-SC linker-exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker-exchange experiments. All the 3D MOFs undergo complete SC-SC transmetalation with Cu(II) , whereby metal exchange in different solvents and monitoring of X-ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis.