Proton Conducting Metal-Organic Frameworks (MOFs) via Post Synthetic Transmetallation and Water Induced Structural Transformations.

Post Synthetic Modification (PSM) of Metal-Organic Frameworks (MOFs) is a crucial strategy for developing new MOFs with enhanced functional properties compared to their parent one. PSM can be accomplished through various methods:1) modification of organic linkers; 2) exchange of metal ions or nodes; and 3) inclusion or exchange of solvent/guest molecules. Herein, PSM of bimetallic and monometallic MOFs containing biphenyl dinitro-tetra-carboxylates (NCA) are demonstrated. The tetra carboxylate NCA, produces monometallic Cd-MOF-1 and Cu-MOF-1 and bimetallic CoZn-MOF in solvothermal reactions with the corresponding metal salts. The CoZn-MOF undergoes post-synthetic transmetallation with Cd(NO3)2 and Cu(NO3)2 in aqueous solution to yield Cd-MOF-2 and Cu-MOF-2, respectively. Additionally, green crystals of Cu-MOF-1 found to undergo a single-crystal-to-single-crystal (SCSC) transformation to blue crystals of Cu-MOF-3 upon dipped into water at room temperature. These MOFs demonstrate notable proton conductivities ranging from 10-3 to 10-4 S cm-1 under variable temperatures and humidity levels. Among them, Cu-MOF-3 achieves the highest proton conductivity of 1.36 × 10-3 S cm-1 at 90 °C and 98% relative humidity, attributed to its continuous and extensive hydrogen bonding network, which provides effective proton conduction pathways within the MOF. This work highlights a convenient strategy for designing proton-conducting MOFs via post-synthetic modification.

Differentiating aliphatic and aromatic alcohols using triazine-based supramolecular organogelators: end group-specific selective gelation with chain length of alcohols.

Supramolecular gels have an extensive range of potential applications, out of which stimuli-responsive materials are a topic of contemporary research. Gels being kinetically entrapped materials can be tuned to different forms using external chemical stimuli. In this context, three different triazine gelators, each containing a unique end group, were examined for gelation in various solvent systems. Nevertheless, the gelation was limited to only alcoholic solvents, suggesting that the hydrogen bonds between the gelating solvent and gelator play a crucial role in gelation. Further, it was found that these gelators could gelate only with aliphatic alcohols, which could be degelled easily using aromatic alcohols. The three gelators exhibited distinct gelation of aliphatic alcohols based on their end groups. The gelator with the polar-aromatic end group (C5H4N) was found to gelate with lighter alcohols, whereas that with the nonpolar aromatic end group (C6H5) was found to prefer higher alcohols. The MGC and Tgel values were also found to depend on the alkyl chain length/branching of the alcohols. The crystal structure of one of the gelators provides insights into the model structure of the gels. Cyclohexanol was the only solvent that could produce gels with all three of the as-synthesised gelators. The process of degelation by aromatic alcohols was monitored at different points of the disassembly process by rheological and morphological measurements to understand the extent of controlled degelation. These gels have great potential for use in controlled drug delivery and chemical sensing, among other areas.

Bimetallic Organic Frameworks via In Situ Solvothermal Sol-Gel-Crystal and Sol-Crystal Transformation as Durable Electrocatalysts for Oxygen Reduction Reaction.

The in situ solvothermal conversion of metal-organic gels (MOGs) to crystalline metal-organic frameworks (MOFs) represents a versatile and ingenious strategy that has been employed for the synthesis of MOF materials with specific morphologies, high yield, and improved functional properties. Herein, we have adopted an in situ solvothermal conversion of bimetallic MOGs to crystalline bimetallic MOFs with the aim of introducing a redox-active metal heterogeneity into the monometallic counterpart. The formation of bimetallic NiZn-MOF and CoZn-MOF via in situ solvothermal sol-gel-crystal and sol-crystal transformation is found to depend on the solvent systems used. The sol-to-gel-to-crystal transformation of NiZn-MOF via the formation of NiZn-MOG is found to occur through the gradual disruption of gel fibers leading to subsequent formation of microcrystals and single crystals of NiZn-MOF. These bimetallic MOFs and MOGs serve as promising electrocatalysts for oxygen reduction reaction (ORR) with an excellent methanol tolerance property, which can be attributed to the enhanced mass and charge transfer, higher oxygen vacancies, and bimetallic synergistic interactions among the heterometals. This work demonstrates a convenient strategy for producing bimetallic MOGs to MOFs through the introduction of a redox-active metal heterogeneity in the inorganic hybrid functional materials for fundamental and applied research. Our results connect MOGs and MOFs which have been regarded as having opposite physical states, that is, soft vs hard, and provide promising structural correlation between MOGs and MOFs at the molecular level.

Comparative Study of Nitro- and Azide-Functionalized ZnII -Based Coordination Polymers (CPs) as Fluorescent Turn-On Probes for Rapid and Selective Detection of H2 S in Living Cells.

Selective detection of H2 S in the cellular systems using fluorescent CPs/MOFs is of great scientific interest due to their outstanding aqueous stability, biocompatibility and real-time detection ability. Fabrication of such materials using complete biologically essential elements and applying them as an efficient biosensor is still quite challenging. In this context, two newly synthesized CPs containing biologically essential metal ion (Zn) and nitro/azido functional groups into the framework to sense extracellular and intracellular H2 S by reducing into respective amines are presented. The CP-1 containing the azide group acted as an efficient fluorescent turn-on probe with the lowest detection limit (7.2 µM) and shortest response time (30 s) among the Zn-based probes reported till date. Moreover, CP-1 exhibited green luminescence in live cells after imaging a very low concentration of H2 S, whereas the nitro analogue CP-2 could not detect the target analyte due to its framework disruption.

Halogen⋠⋠⋠Halogen and Halogen⋠⋠⋠π Interactions Enabled Reversible Photo-oligomerization of Conjugated Dienones: Visible Light Triggered Single-Crystal-to-Single-Crystal Transformation.

The synthesis of reversible oligomer/polymers is fascinating both from the perspective of the fundamental understanding as well as their applications, ranging from biomedical to self-healing smart materials. On the other hand, the reactions that occur in single-crystal-to-single-crystal (SCSC) fashion offer great details of the structure, geometry and stereochemistry of the product. However, SCSC [2+2] oligomerization is rather difficult and rare. Further, till date there are no reports for a reversible [2+2] oligomerization in SCSC fashion. In this work, four halogen-substituted acrylic dienone molecules were deliberately designed and their ability to participate in [2+2] cycloaddition reaction in solid state was studied under visible light. Despite of having the required alignment of double bonds of dienes in all four crystal structures, they were found to exhibit variable reactivities given the differences in their weak intermolecular interactions such as halogen⋅⋅⋅halogen, halogen⋅⋅⋅π and C-H⋅⋅⋅O interactions. Notably, one of these materials exhibits reversible oligomerization in a SCSC manner.

Photoinduced Bending of Single Crystals of a Linear Bis-Olefin via Water-Templated Solid-State [2+2] Photopolymerization Reaction.

The single crystals of two structural isomers of bis-olefinic molecules were shown to have contrasting properties in terms of their photoreactivity: one exhibits an excellent ability to form polymers, accompanied with bending of crystals upon irradiation, while the other is photostable. The photoreactive crystal is a first example in which [2+2] polymerization leads to bending of the crystals, with implications for the design of photoactuators. The hydrate formation ability of one of these molecular isomers promotes the solid-state reactivity in its crystal, as the H2 O molecules act as a template to bring the olefin molecules into the required arrangement for [2+2] polymerization. Further, the crystals of the polymer exhibited better flexibility and smoothed surfaces compared to those of the monomers. In addition, under UV-light the diene emits bluish violet light while the polymer emits green light, indicating that the luminescence property can be tuned through photoirradiation.

Is the origin of green fluorescence in unsymmetrical four-ring bent-core liquid crystals single or double proton transfer?

The origin of green fluorescence in unsymmetrical four-ring bent-core liquid crystals (BCLCs) is not understood clearly. There is no analysis of the photo-physical properties, in particular, the excited state dynamical behaviour, of these molecules. Because of the availability of two proton transfer sites in these systems, there is no clear explanation of the involvement of single or double proton transfer reactions in the origin of the large Stokes shifted green fluorescence band. Therefore, we employ the femtosecond transient absorption spectroscopy technique to recognize the formation of transient species in the excited state and its associated dynamics in the femto-picosecond time domain. In order to validate the experimental photo-physical properties, the time-dependent density functional theory (TDDFT) calculations have been performed. Our results indicate that the four-ring bent-core system is an excellent example of systems exhibiting two proton transfer reactions in a sequential process. Further, these two proton transfer sites are not electronically coupled to each other; therefore, monoketo and diketo tautomers exhibit very close absorption and emission positions. The large Stokes shifted green emission in these systems is mainly contributed by the monoketo tautomer (MK-C*). The linking ester functional group of both sites plays a significant role in controlling the rate of proton transfer reactions. A good correlation is observed between theoretical and experimental results.

Isostructural NiII Metal-Organic Frameworks (MOFs) for Efficient Electrocatalysis of Oxygen Evolution Reaction and for Gas Sorption Properties.

Design and synthesis of stable, active and cost-effective electrocatalyst for water splitting applications is an emerging area of research, given the depletion of fossil fuels. Herein, two isostructural NiII redox-active metal-organic frameworks (MOFs) containing flexible tripodal trispyridyl ligand (L) and linear dicarboxylates such as terephthalate (TA) and 2-aminoterphthalate (H2 NTA) are studied for their catalytic activity in oxygen evaluation reaction (OER). The 2D-layered MOFs form 3D hydrogen bonded frameworks containing one-dimensional hydrophilic channels that are filled with water molecules. The electrochemical studies reveal that MOFs display an efficient catalytic activity towards oxygen evolution reaction in alkaline conditions with an overpotential as low as 356 mV. Further, these 2D-MOFs exhibit excellent ability to adsorb water vapor (180-230 cc g-1 at 273 K) and CO2 (33 cc g-1 at 273 K). The presence of hydrophilic functionality in the frameworks was found to significantly enhance the electrocatalytic activity as well as H2 O sorption.

Isoreticular Expansion of Metal-Organic Frameworks via Pillaring of Metal Templated Tunable Building Layers: Hydrogen Storage and Selective CO2 Capture.

The deliberate construction of isoreticular eea-metal-organic frameworks (MOFs) (Cu-eea-1, Cu-eea-2 and Cu-eea-3) and rtl-MOFs (Co-rtl-1 and Co-rtl-2) has been accomplished based on the ligand-to-axial pillaring of supermolecular building layers. The use of different metal ions resulted in two types of supermolecular building layers (SBLs): Kagome (kgm) and square lattices (sql) which further interconnect to form anticipated 3D-MOFs. The isoreticular expansion of (3,6)-connected Cu-MOFs has been achieved with desired eea-topology based on kgm building layers. In addition, two (3,6)-connected Co-rtl-MOFs were also successfully constructed based on sql building layers. The Cu-eea-MOFs were shown to act as hydrogen storage materials with appreciable amount of hydrogen uptake abilities. Moreover Cu-eea-MOFs have also exhibited remarkable CO2 capture ability at ambient condition compared to nitrogen and methane, due to the presence of amide functionalities.

Porous Metal-Organic Polyhedral Framework containing Cuboctahedron Cages as SBUs with High Affinity for H2 and CO2 Sorption: A Heterogeneous Catalyst for Chemical Fixation of CO2.

Development of active porous materials that can efficiently adsorb H2 and CO2 is needed, due to their practical utilities. Here we present the design and synthesis of an interpenetrated CuII metal-organic framework (MOF) that is thermally stable, highly porous and can act as a heterogeneous catalyst. The CuII -MOF contains a highly symmetric polyhedral metal cluster (Cu24 ) with cuboctahedron geometry as secondary building unit (SBU). The double interpenetration of such huge cluster-containing nets provides a high density of open metal sites, due to which it exhibits remarkable H2 storage capacity (313 cm3 g-1 at 1 bar and 77 K) as well as high CO2 capture ability (159 cm3 g-1 at 1 bar and 273 K). Further, its propensity towards CO2 sorption can be utilized for the heterogeneous catalysis of the chemical conversion of CO2 into the corresponding cyclic carbonates upon reaction with epoxides, with high turnover number and turnover frequency values.

Self-Sorting of Metal-Organic Polymeric Assemblies in Gels: Selective Templation and Catalysis of Homodimers.

The development of generic strategy is essential for the construction of higher order supramolecular assemblies from the mixture of molecular components. Such higher order aggregations are possible through a self-sorting phenomenon, which is not well-explored in gel materials. Here, first examples of self-sorting in the coordination polymer (CP) based gels have been explored using three and four component systems. The self-sorting phenomenon has been monitored through a [2+2] photochemical reaction in the gel state and characterized by 1 H NMR, diffuse reflectance spectroscopy (DRS) and single crystal XRD analyses. Furthermore, AgI was shown to act as a supramolecular catalyst for the [2+2] photochemical reaction in gels.

Origin of green photoluminescence in four-ring bent-core molecules with ESIPT, selective sensing of zinc ions by turn-on emission and their liquid crystal properties.

Fluorescent four-ring symmetrical/unsymmetrical molecules containing alkyl chains of a varied number of -CH2- groups with a bent-core have been synthesized to explore their liquid crystalline (LC) and photophysical properties. Some of these molecules depending upon their alkyl chain length were found to exhibit B1 and B7 liquid crystalline phases and are characterized by various analytical techniques such as FT-IR, 1H NMR, mass, POM, DSC, single crystal XRD, etc. Crystal structure determination reveals the hydrogen bonded enol form of these molecules with non-planar bent-molecular geometry. Intramolecular hydrogen bonding was found to play an important role in the stabilization of these molecules and in the origin of their green photoluminescence (GPL). The photo-physical experimental results through various control experiments clearly demonstrate that the origin of the large Stokes shifted GPL of these molecules can be attributed to the excited state intramolecular proton transfer (ESIPT) process. The formation of various types of anionic species and their stability were explored through steady-state and time-resolved fluorescence measurements. These compounds are found to be good turn-on PL probes in the selective detection of zinc ions at the micromolar level. Upon binding of zinc ions with the bent-core molecule, the structural changes have been investigated through NMR spectroscopy.

Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid-State [2+2]-Photopolymerization.

An organic polymer containing cyclobutanes and amides as backbones and pyridyl groups as sidearms was synthesized by single-crystal-to-single-crystal (SCSC) [2+2]-photopolymerization in the coordination polymers (CPs) of diene. The diene molecule was photo-inactive in its crystals and formed a triply intertwined 1D-helical CP with Cd(NO3 )2 and Cu(NO3 )2 salts. The 1D-CP was transformed into a coordination polymer of organic polymers containing threefold interpenetrated 3D-networks of CdSO4 topology through a [2+2]-reaction in SCSC manner upon irradiation. The organic polymer was separated from its CPs and found to have an unusually high degree of polymerization for this type of reaction. Furthermore, the organic polymer was amenable for N-alkylation reactions such as methylation, propylation, and decylation. The formate salts of the organic polymer and the methylated polymer were shown to form plastic films with a combination of properties such as high transparency, tensile strengths, gas permeability, thermal stability, water-resistance, and resistance to other organic solvents. The methylated polymer was also able to capture chromate ions and anionic dyes from aqueous solutions.

Regiodivergent and short total synthesis of calothrixins.

The anionic annulation of MOM-protected furoindolone with 4-bromoquinoline followed by deprotection of the N-MOM group provides calothrixin B, whereas that with 3-bromoquinoline yields isocalothrixin B. The outcomes are explained by the divergence of the reaction mechanism from commonly perceived quinolyne intermediate. A sequence of addition-cyclization-elimination is proposed to account for the formation of calothrixin from 4-bromoquinoline.

Crystal engineering of topochemical solid state reactions.

Solid state reactions offer a unique opportunity for synthesizing complex molecules with amazing regio- and stereo-specificity otherwise difficult to synthesize by conventional organic synthetic methodologies. In particular, the solid state [2 + 2] reaction is a well studied reaction in terms of a crystal engineering perspective. The main challenge in performing solid state reactions is bringing the molecules into reactive orientations such that the reactive groups are within a certain proximal distance. The out surge in organic and inorganic crystal engineering studies offers several strategies for bringing the molecules together in the crystal lattice. These strategies include from weak interactions (halogen bonds, halogen···halogen, π···π, cation···π) to strong hydrogen bonds (O-H···O, N-H···O, O-H···N and N-H···N) to coordination complexes/polymers. To date many studies are available which use such strategies for conducting single, double, triple or multiple [2 + 2] reactions, [4 + 4] reactions, Diels-Alder reactions and polymerization reactions of acetylene molecules. Some of the crystal engineering strategies include the use of external templates which can be removed after the reaction and some of the other strategies deals with the modification of reactant molecules. In this review, the current status of various strategies will be outlined with respect to the nature of the interactions involved.

Amine Functionalization of Channels of Metal-Organic Frameworks for Effective Chemical Fixation of Carbon Dioxide: A Comparative Study with Three Newly Designed Porous Networks.

Catalytic transformation of CO2 into value-added chemical products can provide an appropriate solution for the raising environmental issues. To date, various metal-organic frameworks (MOFs) with transition metal ions have been explored for CO2 capture and conversion, but alkaline earth metal-based MOFs are comparatively less studied. Metal ions like Sr(II) having relatively large radius give rise to a high coordination number resulting in higher stability of the MOFs. Moreover, the introduction of N-rich functional group in organic linker like -NH2, -CONH- and triazole into MOF backbone enhance their CO2 capture and conversion efficiency. Herein, the effect of amine group on the catalytic efficiency of MOFs for CO2 cycloaddition with epoxides under solvent free and ambient conditions are presented. The di-carboxylates, such as 5-aminoisophthalate (AmIP) and 5-bromoisophthalate (BrIP) were utilized to synthesize Sr(II) based MOFs. The Zn(II) MOF was synthesized using tetra-carboxylate containing amide spacer (OAT) and 4-amino-4H-1,2,4-triazole (AMT). All three MOFs exhibited porous networks with guest available volume ranging from 15 to 58 %. The catalytic efficiency of the MOFs towards carbon dioxide fixation reaction was explored. The catalytic performances revealed that the presence of amine group in the channels enhances the catalytic efficiency of the MOFs.

Photo-responsive metal-organic gels of rigid phenylene-1,3-di-substituted angular dienes with metal halides: gel-to-gel transformations triggered by [2 + 2] polymerization.

Herein, the first report on gel-to-gel transformations via [2 + 2] photopolymerization in MOGs of metal halides and rigid dienes is presented. The MOGs and their xerogels show exceptional ability to undergo [2 + 2] polymerisation upon UV irradiation. Gel-to-gel transformations are very rare as the post-modification of gelators weakens the gel and transforms it to a sol. Such transformations change the molecular assemblies into gels with altered mechanical and chemical properties. These phenomena pave the way to synthesize new MOGs with improved rigidity that cannot be synthesized otherwise.

In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy.

The design of highly efficient, cost-effective non-noble metal-based electrocatalysts with superior stability for overall water splitting (OWS) reactions is of great importance as well as of immense challenge for the upcoming sustainable and green energy conversion technologies. Herein, a convenient and simple in situ solvothermal method has been adopted to fabricate a self-supported, binder-free 3D electrode (Mn-MOF/NF) by the direct growth of a newly synthesized carboxylate-based pristine Mn(II)-metal-organic framework (Mn-MOF) upon the conducting substrate nickel foam (NF). The binder-free Mn-MOF/NF electrode exhibits excellent performances toward OWS with ultralow overpotentials of 280 mV@20 mA cm-2 for the oxygen evolution reaction (OER) and 125 mV@10 mA cm-2 for the hydrogen evolution reaction (HER) with remarkable durability. Mn-MOF/NF can also attain a current density of 10 mA cm-2 with a low cell voltage of 1.68 V in a 0.1 M KOH solution in a two-electrode system for OWS. The direct growth of nonconducting electroactive Mn-MOF materials upon conducting substrate NF provides an excellent mass transport of the electrolyte with a relatively low contact resistance due to the strong catalyst-substrate contact and enhances the efficient electron transport for OWS. The redox chemical etching of the self-sacrificial substrate NF during solvothermal synthesis introduces redox-active Ni2+ in Mn-MOF/NF. Thus, the excellent OWS electrocatalytic activity can mainly be attributed to the bimetallic synergistic collaboration of the two redox active metal centers (Mn2+ and Ni2+) along with the excellent support surface of NF, which provides a high specific surface area and maximum utilization of the electroactive metal ion sites by preventing the self-aggregation of the active sites. The Mn-MOF/NF electrode also exhibits superb stability and durability for a prolonged time throughout the multiple cycles of full water splitting reactions. Therefore, this work elucidates a convenient and smart approach for constructing MOF-based bifunctional electrocatalysts for OWS.

In situ conversion of a MOG to a crystalline MOF: a case study on solvent-dependent gelation and crystallization.

Herein, we report in situ transformation of a metal-organic gel (MOG) to a crystalline metal-organic framework (MOF) and solvent-dependent gelation/crystallization via solvothermal reactions of a tetracarboxylic acid, namely 4,4'-dinitro-2,2',6,6'-tetracarboxybiphenyl, and ZnSO4. The results provide structural insights into MOGs at the molecular level and also help in the synthesis of crystalline MOFs that are otherwise difficult to obtain.

Metal-organic frameworks as proton conductors: strategies for improved proton conductivity.

Recent studies on proton conductivity using pristine MOFs and their composite materials have established an outstanding area of research owing to their potential applications for the development of high performance solid state proton conductors (SSPCs) and proton exchange membranes (PEMs) in fuel cells (FCs). MOFs, as crystalline organic and inorganic hybrid materials, provide a large number of degrees of freedom in their framework composition, coordination environment, and chemically functionalized pores for the targeted design of improved proton carriers, functioning over a wide range of temperature and humidity conditions. Herein, our efforts have been emphasized on fundamental principles and different design strategies to achieve enhanced proton conductivity with appropriate examples. We also have discussed the modification mechanism of MOF-composite materials and mixed matrix membranes for commercial applications in FCs. Thus, this review aims to direct readers' attention towards the design strategies and structure-property relationship for proton transport in MOFs.