Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO2 Fixation.

Continuous increase in carbon dioxide (CO2) emissions are causing imbalances in the environment, which impact biodiversity and human health. The conversion of CO2 to cyclic carbonates by means of metal-organic frameworks (MOFs) as a heterogeneous catalyst is a prominent strategy for rectifying this imbalance. Herein, we have developed nitrogen-rich Zn (II) based metal-organic framework, [Zn(CPMT)(bipy)]n (CPMT = 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole; bipy = 4,4'-bipyridine), synthesized via a mixed ligand strategy. This Zn-MOF showed high chemical stability in both acidic and basic conditions, and in organic solvents for a long time. On account of the concurrent presence of acid-base active sites and strong chemical stability under abrasive conditions, this Zn-MOF was employed as an effective catalyst for the coupling of CO2 and epoxides, under atmospheric pressure, mild temperature, and neat conditions. This Zn-MOF shows remarkable activity by producing high yields of epichlorohydrin carbonate (98%) and styrene carbonate (82%) at atmospheric CO2 pressure, 70 °C temperature, and 24 h reaction time, with turnover numbers (TON) of 217 and 181, respectively. The Zn-MOF could be reused for up to seven cycles with structural and framework integrity. Overall, this work demonstrates the synthesis of a novel and highly efficient MOF for CO2 conversion.

Amino Acid-Based Molecular and Membranous Chiral Tools for Enantiomeric Recognition.

Given the need, both academic and industrial, for new approaches and technologies for chiral discrimination of enantiomers, the present work demonstrates the development through rational design and integration of two new chiral platforms (molecular and membranous) for enantioselective recognition through visual as well as microscopic observation. The molecular platform (TPT) is based on the tryptophan derivative developed through the condensation of two tryptophan units with terepthaloyl chloride. While TPT based on l-tryptophan recognizes R-mandelic acid over the S-isomer, the host with reverse chirality (TPDT) recognizes S-mandelic acid over R-isomer. The role of chemical functionality in this sensitive recognition process was established experimentally by developing an analogue of TPT and by judiciously using different chiral analytes. Importantly, a detailed theoretical study at the molecular level revealed the U-shaped conformation of TPT, creating a cavity for accommodating a chiral guest with selective functional interaction resulting in the discrimination of enantiomers. Finally, a chiral polymeric mat of poly(methyl methacrylate) (PMMA)/polyacrylonitrile (PAN) (2:3) impregnated with TPT was developed via electrospinning. The resulting fibrous mat was successfully utilized for chiral recognition through microscopic and architectural observation. Hence, the present work reports simple chiral tools for enantiomeric recognition.

NiFe-Coordination Polymers-Derived Layered Double Hydroxides as Bifunctional Materials: Effect of the Ni : Fe Ratio on the Electrochemical Performance.

The development of an efficient and cost-effective material is highly desirable for electrochemical devices such as electrolyzers and supercapacitors. Especially, pseudomorphic transformations of metal-organic frameworks (MOFs)/coordination polymers (CPs) into layered double hydroxides (LDHs) materials endow well-defined porosities, high surface area, exchangeable interlayer anions and easily adjustable electronic structure that are truly required for oxygen evolution reaction (OER) and high-performance supercapacitor applications. Herein, we have prepared NiFe-LDHs of various Ni/Fe ratios via a facile room-temperature alkaline hydrolysis of NiFe-CPs precursors. Electrochemical studies reveal that the catalyst having high amount of Fe (Ni1.2 Fe1 -LDH) showed the better OER activity with a low Tafel slope (65 mV dec-1 ) in 1 M KOH. On the other hand, the catalyst containing higher amount of Ni with better layered structure (Ni11.7 Fe1 -LDH) showed high performance for supercapacitor (702 F g-1 at 0.25 A g-1 ) in 3 M KOH. Moreover, a solid-state asymmetric supercapacitor device Ni11.7 Fe1 -LDH/AC was fabricated which exhibited a specific capacitance of 18 F g-1 at a current density of 1 A g-1 . The device displayed high cycling stability with 88% of capacitance retention after 7000 cycles. The experimental findings in this work will help in the futuristic development of NiFe-LDH based electrocatalysts for the enhanced electrochemical performances.

Amino decorated adenine based metal-organic framework for multi-faceted applications.

Multifunctional metal-organic frameworks with luminescence properties are promising materials for the detection and treatment of toxic pollutants in aqueous media. Herein, an adenine-based multifunctional Zn-MOF {[Zn3.5(AIPA)2(Ade)3(H2O)2]n using linkers adenine (Ade) and 5-aminoisophthalic acid (AIPA)} was prepared that could selectively detect particular classes of explosives and antibiotics, namely, nitrophenols, tetracyclines and nitrofurans. Moreover, the as-synthesized Zn-MOF displayed a remarkable efficiency for the treatment of antibiotics in water through adsorption and photocatalytic degradation. A subtle balance between photoinduced electron transfer (PET), resonance energy transfer (RET) and competitive excitation energy absorption enabled detection selectivity towards the pollutants. On the other hand, intermolecular interactions of free functional groups assisted the treatment process and thereby highlighted the crucial role of the linkers in furnishing multifunctional behavior without the need for any postsynthetic modifications.

Cu(II)-Based Coordination Polymer as a Pristine Form Usable Electrocatalyst for Oxygen Reduction Reaction: Experimental Evaluation and Theoretical Insights into Biomimetic Mechanistic Aspects.

As the postsynthesis-processed metal-organic material-based catalysts for energy applications add additional cost to the whole process, the importance of developing synthesized usable pristine catalysts is quite evident. The present work reports a new Cu-based coordination polymer (Cu-CP) catalyst to be used in its pristine form for oxygen reduction reaction (ORR) application. The catalyst was characterized using single-crystal X-ray diffraction, field emission scanning electron microscopy, and X-ray photoemission spectroscopy. The Cu-CP exhibits admirable electrocatalytic ORR activity with an onset potential of 0.84 V versus RHE and a half wave potential of 0.69 V versus RHE. As revealed by the density functional theory-based computational mechanistic investigation of the electrocatalytic ORR process, the electrochemically reduced Cu(I) center binds to the molecular O2 through an exergonic process (ΔG = -6.8 kcal/mol) and generates the Cu(II)-O2•- superoxo intermediate. Such superoxo intermediates are frequently encountered in the catalytic cycle of the Cu-containing metalloenzymes in their O2 reduction reaction. This intermediate undergoes coupled proton and electron transfer processes to give OH- in an alkaline medium involving H2O2 as the intermediate. The electrocatalytic performance of Cu-CP remained stable even up to 3000 cycles. Overall, the newly developed Cu-CP-based electrocatalyst holds promising potential for efficient biomimetic ORR reactivity, which opens new possibilities toward the development of robust coordination polymer-based electrocatalysts.

Recent advances in the metal-organic framework-based electrocatalysts for trifunctional electrocatalysis.

The sustainable energy technology is in great demand due to the depletion and the risks associated with the use of fossil fuels. Various energy technologies like regenerative fuel cells, zinc-air batteries, and overall water-splitting devices have a huge scope in the growth of green energy. The efficiency of these devices is reliant upon the multifunctional electrocatalysts, which include both bifunctional and trifunctional electrocatalysts. Among the different categories of the materials used for such multifunctional electrocatalysis, metal-organic-frameworks (MOFs) occupy a very consolidated place because of their high surface area, porosity, and many other unique physicochemical properties. However, the use of MOFs for the trifunctional electrocatalytic applications is in the budding phase and needs to be explored more. Further, most of these MOF-based trifunctional electrocatalysts are derived by pyrolyzing MOFs at high temperatures. Therefore, there is a need to develop more conductive MOFs which can be directly utilized for the trifunctional applications. In this frontier article, we present the latest reports on the MOF-based materials for trifunctional applications. The material design strategies of the MOF-based materials for trifunctional electrocatalysis have been discussed. The progressive improvements made with MOFs in electrocatalytic applications have been provided with emphasis on the structural, active site and compositional requirements. Finally, the challenges and viewpoints on the future development of the MOF-based materials for trifunctional electrocatalysis have been provided.

Chiral gelators for visual enantiomeric recognition.

Introduction of chirality in supramolecular gels has allowed the effective translation and amplification of molecular chirality. Upon integrating the stimuli-responsive nature of these gels with supramolecular chirality, a new platform for the discrimination of the enantiomeric guests through naked eye can be developed. Over the past decade, several groups have reported the development of chiral supramolecular gels for enantioselective recognition through gel formation or collapse. However, to the best of our knowledge, we are yet to come across a review highlighting the utilization of chiral supramolecular gels for macroscopic discrimination of enantiomers. In this article, we have articulated the chiral gelators developed to date for the recognition of different enantiomeric analytes focusing on their mode of recognition with an in-depth analysis of the mechanism of interactions assisting the recognition process.

Coordination networks for the recognition of oxo-anions.

Crystalline coordination networks with an infinite extended framework, also known as coordination polymers (CPs) or metal-organic frameworks (MOFs), have attracted significant attention owing to their tremendous performance in an extensive range of applications. The unique structural features and high stability of coordination networks are responsible for their utilization and potential in diverse fields especially in the area of sensing using luminescent CPs/MOFs. The recognition of toxic oxo-anions present in water is a crucial and first step towards environmental remediation, mainly in the case of water pollution. Accordingly, the utilization of luminescent coordination networks has received significant interest, particularly for the recognition of various toxic oxo-anions, which are considered a threat to aquatic life and the environment. In this frontier article, we summarize recent reports on luminescent CPs/MOFs, their utilization for the sensing of oxo-anions and the chemistry of the interaction of oxo-anions with CPs/MOFs, which is responsible for tuning their optical signals.

Molecular-level insights into the self-assembly driven enantioselective recognition process.

The importance of the orientation of functional groups in a chiral environment on enantioselective recognition has been demonstrated. Orientation controlled interactions of functional groups in (R)/(S)-MA lead to a visually differentiable morphology with an arginine-based gelator. The crucial role of various molecular-level interactions discriminating the enantioselective self-assembly has been established using different analytical techniques, crystal structure analysis, and DFT calculations.

Zn(ii)-based coordination polymer: An emissive signaling platform for the recognition of an explosive and a pesticide in an aqueous system.

A new emissive Zn(ii)-based coordination polymer (Zn-CP) bearing paddle-wheel clusters has been developed and the same has been demonstrated to have potential for recognising a nitroaromatic-based explosive (TNP) and a pesticide (2,6-DCNA) in aqueous solution. The structural integrity of this newly developed 2D material was established through single-crystal analysis, whereas the stability of Zn-CP in aqueous medium after the recognition process was investigated by the powder-XRD technique. A combination of experimental and theoretical studies revealed that the change in fluorescence intensity of Zn-CP while interacting with TNP and 2,6-DCNA was possibly due to simultaneous operation of PET and FRET. Experimentally, it was also established that Zn-CP can be reused in up to three cycles for the detection of TNP and 2,6-DCNA.

Trifunctional metal-organic platform for environmental remediation: structural features with peripheral hydroxyl groups facilitate adsorption, degradation and reduction processes.

A Cd(ii)-based metal-organic framework (MOF) {[Cd(PA)(4,4'-bpy)2](H2O)}n (where, PA = pamoic acid, and bpy = bipyridine) has been demonstrated to have trifunctional properties, namely as (i) an efficient and selective adsorbent for dyes, (ii) a visible-light-active photocatalyst for the degradation of dyes and (iii) a photocatalyst for Cr(vi) reduction. Hence, this material has a very good potential for application in environmental remediation. In particular, the MOF exhibits excellent selectivity toward cationic methylene blue (MB) dye adsorption and its separation over neutral (neutral red) and anionic (methyl orange) dyes. In addition, the catalyst has also been explored for the photocatalytic degradation of less adsorbed dyes, such as methyl orange (MO) and rhodamine B (RhB). Subsequently, the potential of the presented MOF for the photocatalytic reduction of Cr(vi) under visible light irradiation has also been investigated and the catalyst was found to reduce 95% of Cr(vi) within 3 h. Moreover, simultaneous one-pot photocatalytic reduction of Cr(vi) and dye degradation has been demonstrated with high efficiency using the same catalyst. The mechanism of adsorption could be correlated to the presence of peripheral hydroxyl groups in the MOF and the photocatalytic activity observed under visible light could be attributed to the optical properties of Cd-MOF. In principle, this work could broaden the utilization of single metal organic platform for multifunctional applications toward environmental remediation.

Preferential intermolecular interactions lead to chiral recognition: enantioselective gel formation and collapse.

Interesting self-assembly of an amino acid based molecular material into a hydrogel in the presence of selective enantiomeric chiral amines leading to chiral recognition has been demonstrated. Moreover, collapse of a metallogel formed from the same material in the presence of selective enantiomers validated its enantioselective affinity. Importantly, in addition to relevant experimental techniques, DFT studies have been successfully explored to establish chiral recognition through enantioselective gelation.

A Polycarboxyl-Decorated FeIII -Based Xerogel-Derived Multifunctional Composite (Fe3 O4 /Fe/C) as an Efficient Electrode Material towards Oxygen Reduction Reaction and Supercapacitor Application.

Low cost, non-noble metal catalysts with a good oxygen reduction reaction (ORR) activity comparable to that of platinum and also having good energy storage properties are highly desirable but challenging. Several challenges are associated with the development of such materials. Herein, we demonstrate a new polycarboxyl-functionalised FeIII -based gel material, synthesised following a solvothermal method and the development of its composite (Fe3 O4 /Fe/C) by annealing at optimised temperature. The developed composite displayed excellent electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.87 V (vs. RHE) and a current density value of -5 mA cm-2 , which are comparable with commercial 20 wt % Pt/C. In addition, as one of the most desirable properties, the composite exhibits a better methanol tolerance and greater durability than Pt/C. The same material was explored as an energy storage material for supercapacitors, which showed a specific capacitance of 245 F g-1 at a current density of 1 A g-1 . It is expected that this Fe3 O4 /Fe/C composite with a disordered graphitised carbon matrix will pave a horizon for developing energy conversion and energy storage devices.

A metal-organic framework based multifunctional catalytic platform for organic transformation and environmental remediation.

Given the need for an efficient reaction platform, a multifunctional material has been developed through the integration of iodine into a Cd2+ based MOF as a new catalytic system for organic transformation. Furthermore, the Cd-MOF itself has been successfully used as a potential material for photocatalytic dye degradation. The iodine incorporated MOF showed tremendous efficiency in organic catalysis for the synthesis of a library of benzimidazole derivatives with yield >80%. In addition, the same iodine loaded MOF (I2@Cd-MOF) exhibits good applicability and reusability for the synthesis of thienyldipyrromethane. Apart from this, the photocatalytic activity of the Cd-MOF was also evaluated under visible light irradiation which revealed excellent photocatalytic activity (82%) for MB degradation without the use of any enhancers. Altogether, this catalytic platform established its efficacy as a multifunctional catalyst in the organic synthesis of biologically active motifs and photocatalytic dye degradation.

A long-range emissive mega-Stokes inorganic-organic hybrid material with peripheral carboxyl functionality for As(v) recognition and its application in bioimaging.

We demonstrate a strategy for the recognition of As5+ in aqueous solution using a red-emissive probe based on a perylene-Cu2+ ensemble decorated with peripheral free carboxyl functionality. Single crystal analysis helped us to understand the chemical structure of the probe. To the best of our knowledge, this is the first probe for arsenic detection which emits in the red region (λem = 600 nm). The perylene-Cu2+ ensemble exhibited a mega-Stokes shift (>100 nm) with a high degree of selectivity upon interaction with As5+, which indicated that the present probe has the potential to be used as a turn-on optical sensor for selective detection of As5+ with fewer experimental limitations. The detection limit was found to be 26 nM. Inspired by its good emissive properties, the ensemble was further explored for imaging As5+ in live cells. Because of its long-range emissive nature, no autofluorescence from the cellular species was observed during the imaging process. The probe was evaluated to be non-toxic and successfully permeated the cell membrane without the help of any permeabilizing agent to image As5+.

Highly Directional 1D Supramolecular Assembly of New Diketopyrrolopyrrole-Based Gel for Organic Solar Cell Applications.

A new thermoreversible organogel based on diketopyrrolopyrrole dye (DPP-NCO) is reported for the first time and evolved as a new building block for the fabrication of 1D supramolecular assembly. AFM analysis illustrated that its gel state is composed of different sized 1D rods. DPP-NCO gel used as an additive in organic solar cells yields high efficiency of 7.9% owing to better nanophase separation of its active layer.

Novel metal-organic framework with tunable fluorescence property: supramolecular signaling platform for polynitrophenolics.

With the aid of a rotational C3-symmetric tricarboxytriphenylamine based ligand, a new Cd-MOF was synthesized and characterized by various spectroscopic techniques as well as by single-crystal X-ray diffraction analysis. The structural investigation of the crystalline Cd-MOF complex revealed the existence of unique three symmetry independent coordination environments of Cd(ii) ions with common octahedral and pentagonal bipyramidal geometries. Small cavities with dimensions 6.40 Å × 6.41 Å were present in the crystal system. The tunable fluorescence property of the complex was explored to detect selectively polynitrophenol based explosive materials in the presence of other nitro explosives such as RDX, HMX, TNT and so on. Thermogravimetric analysis and powder X-ray diffraction data support the high thermal stability and crystallinity of the complex.

Turn-on trivalent cation selective chemodosimetric probe to image native cellular iron pools.

A new turn-on cell permeable chemodosimetric probe has been developed and its application in the selective detection of trivalent cations (Fe(3+)/Cr(3+)/Al(3+)) at a sub-nanomolar level has been demonstrated. The selectivity of over a broad spectrum of mono- and divalent metal ions was established using fluorescence spectroscopy. Moreover, the changes in the absorption spectra of in the presence of trivalent cations enabled the most bio-relevant metal ion Fe(3+) over Cr(3+)/Al(3+) to be distinguished. The probe was found to be successful in the fluorescence imaging of native cellular iron pools. The fluorescence imaging of the native iron pools of banana pith further supported the high sensitivity of towards Fe(3+) present in living systems. To the best of our knowledge, this is the first example of a turn-on chemodosimetric probe to image native cellular Fe(3+) pools.

Sodium and potassium ion directed self-assembled multinuclear assembly of divalent nickel or copper and L-leucine derived ligand.

L-leucine derived ligand (H(2)L(L-leu)), KOH, and Ni(II) salt in 2:2:1 ratio self-assembled into a rather large (approximately 13 A) supramolecular assembly with the formula [K{Ni(HL(L-leu))(2)}(3)](+) (1). Structural characterization showed three [Ni(HL(L-leu))(2)] units encapsulated K(+) similar to organic crown ethers/cryptand. Substituting Ni(II) with Cu(II) and K(+) with Na(+) in the above reaction resulted in a set of structurally identical assemblies with the general formula [M'{M(HL(L-leu))(2)}(3)](+), where M' is either K(+) or Na(+) and M is either Cu(II) or Ni(II); [Na{Ni(HL(L-leu))(2)}(3)]ClO(4) (2), Na{Ni(HL(L-leu))(2)}(3)]OTf (3), [K{Cu(HL(L-leu))(2)}(3)]ClO(4) (4), [Na{Cu(HL(L-leu))(2)}(3)]ClO(4) (5), [K{Cu(HL(L-leu))(2)}(3)]NO(3) (6). Electrospray Ionization (ESI)-mass spectra of the assemblies in MeOH showed the retention of assemblies in solution. Visible spectroscopic studies showed retention of assembly 1 in N,N-dimethylformamide (DMF) which is stable even after the addition of 5 equiv of [18]-crown-6. The assemblies in 2-6 show various degrees of dissociation to [M(HL(L-leu))(2)] and M', in stronger H-bonding methanol. The dissociation can be reversed upon addition of excess KNO(3)/NaNO(3) salt. Structural characterization of [Cu(HL(L-leu))(2)(MeCN)] (7) along with its transformation to [K{Cu(HL(L-leu))(2)}(3)](+) in the presence of K(+) salt demonstrated that the assembly formation proceeds through an alkali metal ion induced ligand reorientation within the [Cu(HL(L-leu))(2)] units which is further stabilized by six strong H-bonds holding the assembly. Interestingly, visible spectra of 1 and 2 shows that minor structural changes caused by replacing K(+) with Na(+) is sufficient to shift the d-d transition of Ni(II) by approximately 70 nm, thereby providing an indirect way of distinguishing K(+) and Na(+), none of which have spectroscopic signature in the visible range.

Cu(II)-mediated synthesis of a new fluorescent pyrido[1,2-a]quinoxalin-11-ium derivative.

Quinoxalines are heterocyclic compounds with potential application as drugs or fluorophores. However, few quinoxalinylium salts have been reported in the literature. This manuscript describes the synthesis and structural characterization of a previously unknown quinoxalinylium derivative, 2-aminopyrido[1,2-a]quinoxalin-11-ylium ([1](+)), as perchlorate and thiocyanate salts from the Cu(II)-mediated reaction of a Schiff base. The reaction is most efficient with Cu(II). The formation of a small quantity was observed spectroscopically in the presence of either a strong oxidizer or Mn (II). No product formation was observed with Zn(II), Cd(II), Fe(II), or Ni(II). [1](+) emits at 580 nm, with a quantum yield estimated as 0.23, upon excitation at 470 nm.