01487nas a2200301 4500008004100000022001400041245009700055210006900152260007500221300001400296520043700310653001700747653001800764653001700782653000900799653001700808653002000825100002200845700001600867700003000883700002000913700002300933700002600956700002200982700002901004700002101033856013101054 2015 eng d a1434-193X00aIdentifying solid luminogens through gold-catalysed intramolecular hydroarylation of alkynes0 aIdentifying solid luminogens through goldcatalysed intramolecula aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcAUG a4860-48673 a

The identification of a new class of luminogens based on pyrrolo-quinoxaline embedded coumarin (PQC) structures is reported. The reaction relies on the gold-catalyzed hydroarylation reaction of appropriately substituted aryl alkynoates that produces molecules that exhibit solvatochromism and aggregation-induced emission enhancement (AIEE) phenomena. The application of PQCs for live cell imaging has also been demonstrated.

10aCell imaging10aDyes/pigments10afluorescence10aGold10aLuminescence10aSolvatochromism1 aShaikh, Aslam, C.1 aShalini, S.1 aVaidhyanathan, Ramanathan1 aMane, Manoj, V.1 aBarui, Ayan, Kumar1 aPatra, Chitta, Ranjan1 aVenkatesh, Yeduru1 aBangal, Prakriti, Ranjan1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/identifying-solid-luminogens-through-gold-catalysed-intramolecular-hydroarylation-alkynes-000989nas a2200265 4500008004100000022001400041245009700055210006900152260006700221300001200288490000600300653001500306653003300321653002300354653002200377653002900399100002200428700002400450700002000474700002900494700002000523700002400543700003000567856012600597 2015 eng d a2196-735000aLithium-assisted proton conduction at 150 degrees C in a microporous triazine-phenol polymer0 aLithiumassisted proton conduction at 150 degrees C in a micropor a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcNOV a15003010 v210aconduction10ahydrophobic polar frameworks10alithiated polymers10aproton conduction10atriazine-phenol polymers1 aNandi, Shyamapada1 aDhavale, Vishal, M.1 aShalini, Sorout1 aWerner-Zwanziger, Ulrike1 aSingh, Harpreet1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/lithium-assisted-proton-conduction-150-degrees-c-microporous-triazine-phenol-polymer-101806nas a2200205 4500008004100000022001400041245010400055210006900159260000900228300001000237490000600247520107000253100002101323700002201344700002001366700002501386700002801411700003001439856013101469 2015 eng d a2045-232200aPd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation0 aPd loaded amphiphilic COF as catalyst for multifold Heck reactio cJUN  a108760 v53 a

COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd-0 nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) < 0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using `non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 degrees C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

1 aMullangi, Dinesh1 aNandi, Shyamapada1 aShalini, Sorout1 aSreedhala, Sheshadri1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/pd-loaded-amphiphilic-cof-catalyst-multi-fold-heck-reactions-c-c-couplings-and-co-oxidation01828nas a2200181 4500008004100000245013300041210006900174260000800243300001400251520110400265100002001369700002401389700002301413700001801436700003201454700003001486856013001516 2016 eng d00a10000-Fold enhancement in proton conduction by doping of cesium ions in a proton-conducting zwitterionic metal-organic framework0 a10000Fold enhancement in proton conduction by doping of cesium i cSEP a4382-43863 aDeveloping metal-organic framework (MOF)-based proton-conducting electrolytes for fuel-cell applications is an important target that has drawn a lot of attention. A key approach involves the selective replacement of the guest species within the pores to enhance performance. The modular and crystalline nature of the MOF permits controlled introduction of such species and characterization of their compositions with high precision, a task which is very difficult to achieve in amorphous polymers. Herein, we partially replaced the protons of a zwitterionic pyridinol in Mg(terephthalate)(pyridinol) MOF 1 with Cs+ ions, which brought about a 10000-fold increase in the proton conductivity (10(-6) to 10(-2) S cm(-1)). Interestingly, Li+ ions could not be loaded, whereas Cs+ ions with smaller hydrated ionic radii could be loaded, and the loading was controlled as a function of time. The Cs+ loading nearly halved the activation energy (from 0.35 for 1 to 0.19 eV for _Cs). The highest conductivities were realized for an optimal loading of Cs+ ions, which was found to be about 10 % in this case.1 aShalini, Sorout1 aAggarwal, Shubhangi1 aSingh, Santosh, K.1 aDutt, Malvika1 aAjithkumar, Thallaseril, G.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/10000-fold-enhancement-proton-conduction-doping-cesium-ions-proton-conducting-zwitterionic01386nas a2200205 4500008004100000022001400041245011200055210006900167260009000236300001000326490000600336520055300342100002000895700002400915700002900939700002400968700003200992700003001024856012601054 2016 eng d a2045-232200a1000-fold enhancement in proton conductivity of a MOF using post-synthetically anchored proton transporters0 a1000fold enhancement in proton conductivity of a MOF using posts aMACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLANDbNATURE PUBLISHING GROUPcAUG a324890 v63 a

Pyridinol, a coordinating zwitter-ionic species serves as stoichiometrically loadable and non-leachable proton carrier. The partial replacement of the pyridinol by stronger hydrogen bonding, coordinating guest, ethylene glycol (EG), offers 1000-fold enhancement in conductivity (10(-6) to 10(-3) Scm(-1)) with record low activation energy (0.11 eV). Atomic modeling coupled with C-13-SSNMR provides insights into the potential proton conduction pathway functionalized with post-synthetically anchored dynamic proton transporting EG moieties.

1 aShalini, Sorout1 aDhavale, Vishal, M.1 aEldho, Kavalakal, Mathai1 aKurungot, Sreekumar1 aAjithkumar, Thalasseril, G.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/1000-fold-enhancement-proton-conductivity-mof-using-post-synthetically-anchored-proton02149nas a2200217 4500008004100000245017900041210006900220260000800289300001600297490000600313520130400319100002001623700001801643700001701661700002201678700003001700700001601730700002901746700002901775856012701804 2016 eng d00aCO2 Laser direct written MOF-based metal-decorated and heteroatom-doped porous graphene for flexible all-solid-state microsupercapacitor with extremely high cycling stability0 aCO2 Laser direct written MOFbased metaldecorated and heteroatomd cNOV a31841-318480 v83 aOver the past decade, flexible and wearable microelectronic devices and systems have gained significant importance. Because portable power source is an essential need of such wearable devices, currently there is considerable research emphasis on the development of planar interdigitated micro energy-torage devices by employing diverse precursor materials to obtain functional materials (functional carbon, oxides, etc.) with the desirable set of properties. Herein we report for the first time the use of metal organic framework (MOF) and zeolitic imidazolate framework (ZIF-67) for high-wavelength photothermal laser direct writing of metal-decorated, heteroatom-doped, porous few-layer graphene electrodes for microsupercapacitor application. We argue that the specific attributes of MOF as a precursor and the high-wavelength laser writing approach (which creates extremely high localized and transient temperature (>2500 degrees C) due to strong absorption by lattice vibrations) are together responsible for the peculiar interesting properties of the carbon material thus synthesized, thereby rendering extremely high cycling stability to the corresponding microsupercapacitor device. Our device exhibits near 100% retention after 200 000 cycles as well as stability under 150 degrees bending.1 aBasu, Aniruddha1 aRoy, Kingshuk1 aSharma, Neha1 aNandi, Shyamapada1 aVaidhyanathan, Ramanathan1 aRane, Sunit1 aRode, Chandrashekhar, V.1 aOgale, Satishchandra, B. uhttps://library.ncl.res.in/content/co2-laser-direct-written-mof-based-metal-decorated-and-heteroatom-doped-porous-graphene02113nas a2200229 4500008004100000022001400041245008000055210006900135260000900204300002300213490000600236520133300242100002201575700002601597700002101623700002701644700001801671700002801689700002401717700003001741856011201771 2016 eng d a1614-683200aLow band gap benzimidazole COF supported Ni3N as highly active OER catalyst0 aLow band gap benzimidazole COF supported Ni3N as highly active O cDEC  aArticle No:16011890 v63 a

Covalent organic frameworks (COFs) have structures and morphologies closely resembling graphenes, whose modular construction permits atomiclevel manipulations. This, combined with their porous structure, makes them excellent catalyst supports. Here, the high electrocatalytic activity of a composite, formed by supporting Ni3N nanoparticles on a benzimidazole COF, for oxygen evolution reaction is shown. The composite oxidizes alkaline water with a near-record low overpotential of 230 mV @ 10 mA cm(-2) (eta(10)). This high activity is attributed to the ability of the COF to confine the Ni3N nanoparticles to size regimes otherwise difficult to obtain and to its low band gap character (1.49 eV) arising from the synergy between the conducting Ni3N nanoparticles and the pi-conjugated COF. The COF itself, as a metalfree self-standing framework, has an oxygen evolution reaction activity with 10 of 400 mV. The periodic structure of the COF makes it serve as a matrix to disperse the catalytically active Ni3N nanoparticles favoring their high accessibility and thereby good charge-transport within the composite. This is evident from the amount of O-2 evolved (230 mmol h(-1) g(-1)), which, to the best of our knowledge, is the highest reported. The work reveals the emergence of COF as supports for electrocatalysts.

1 aNandi, Shyamapada1 aSingh, Santosh, Kumar1 aMullangi, Dinesh1 aIllathvalappil, Rajith1 aGeorge, Leena1 aVinod, Chathakudath, P.1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/low-band-gap-benzimidazole-cof-supported-ni3n-highly-active-oer-catalyst02259nas a2200229 4500008004100000022001400041245013200055210006900187260007500256300002400331490000600355520136500361100002101726700002401747700002001771700002201791700001801813700001301831700002401844700003001868856013101898 2016 eng d a1614-683200aLow-overpotential electrocatalytic water splitting with noble-metal-free nanoparticles supported in a sp(3) n-rich flexible COF0 aLowoverpotential electrocatalytic water splitting with noblemeta aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcJUL aArticle No. 16001100 v63 a

Covalent organic frameworks (COFs) are crystalline organic polymers with tunable structures. Here, a COF is prepared using building units with highly flexible tetrahedral sp(3) nitrogens. This flexibility gives rise to structural changes which generate mesopores capable of confining very small (<2 nm sized) non-noble-metal-based nanoparticles (NPs). This nanocomposite shows exceptional activity toward the oxygen-evolution reaction from alkaline water with an overpotential of 258 mV at a current density of 10 mA cm(-2). The overpotential observed in the COF-nanoparticle system is the best in class, and is close to the current record of approximate to 200 mV for any noble-metalfree electrocatalytic water splitting system-the Fe-Co-Ni metal-oxide-film system. Also, it possesses outstanding kinetics (Tafel slope of 38.9 mV dec(-1)) for the reaction. The COF is able to stabilize such small-sized NP in the absence of any capping agent because of the COF-Ni(OH)(2) interactions arising from the N-rich backbone of the COF. Density-functional-theory modeling of the interaction between the hexagonal Ni(OH)(2) nanosheets and the COF shows that in the most favorable configuration the Ni(OH)(2) nanosheets are sandwiched between the sp(3) nitrogens of the adjacent COF layers and this can be crucial to maximizing their synergistic interactions.

1 aMullangi, Dinesh1 aDhavale, Vishal, M.1 aShalini, Sorout1 aNandi, Shyamapada1 aCollins, Sean1 aWoo, Tom1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/low-overpotential-electrocatalytic-water-splitting-noble-metal-free-nanoparticles-supported02509nas a2200241 4500008004100000245014200041210006900183260000800252300001400260490000700274520163100281100001701912700002401929700002401953700001601977700001701993700001902010700003502029700002202064700003002086700002402116856012702140 2017 eng d00aSecondary interactions arrest the hemiaminal intermediate to invert the modus operandi of schiff base reaction: a route to benzoxazinones0 aSecondary interactions arrest the hemiaminal intermediate to inv cAPR a4342-43510 v823 aDiscovered by Hugo Schiff, condensation between amine and aldehyde represents one of the most ubiquitous reactions in chemistry. This classical reaction is widely used to manufacture pharmaceuticals and fine chemicals. However, the rapid and reversible formation of Schiff base prohibits formation of alternative products, of which benzoxazinones are an important class. Therefore, manipulating the reactivity of two partners to invert the course of this reaction is an elusive target. Presented here is a synthetic strategy that regulates the sequence of Schiff base reaction via weak secondary interactions. Guided by the computational models, reaction between 2,3,4,5,6-pentafluoro-benzaldehyde with 2-amino-6methylbenzoic acid revealed quantitative (99%) formation of 5-methyl-2-(perfluoropheny01,2-dihydro-4H-benzo[d][1,3]oxazin-4-one (15). Electron donating and electron withdrawing ortho-substituents on 2-aminobenzoic acid resulted in the production of benzoxazinones 936. The mode of action was tracked using low temperature NMR, IN vis spectroscopy, and isotopic (O-18) labeling experiments. These spectroscopic mechanistic investigations revealed that the hemiaminal intermediate is arrested by the hydrogen-bonding motif to yield benzoxazinone. Thus, the mechanistic investigations and DFT calculations categorically rule out the possibility of in situ imine formation followed by ring-closing, but support instead hydrogen-bond assisted ring-closing to prodrugs. This unprecedented reaction represents an interesting and competitive alternative to metal catalyzed and classical methods of preparing benzoxazinone.1 aPatel, Ketan1 aDeshmukh, Satej, S.1 aBodkhe, Dnyaneshwar1 aMane, Manoj1 aVanka, Kumar1 aShinde, Dinesh1 aRajamohanan, Pattuparambil, R.1 aNandi, Shyamapada1 aVaidhyanathan, Ramanathan1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/secondary-interactions-arrest-hemiaminal-intermediate-invert-modus-operandi-schiff-base02343nas a2200217 4500008004100000245013000041210006900171260000800240300002800248490000600276520153100282100002101813700001801834700002201852700002601874700002301900700001801923700002501941700003001966856012901996 2018 eng d00aHigh and reversible lithium ion storage in self-exfoliated triazole-triformyl phloroglucinol-basedcovalent organic nanosheets0 aHigh and reversible lithium ion storage in selfexfoliated triazo cMAR aArticle Number: 17021700 v83 aCovalent organic framework (COF) can grow into self-exfoliated nanosheets. Their graphene/graphite resembling microtexture and nanostructure suits electrochemical applications. Here, covalent organic nanosheets (CON) with nanopores lined with triazole and phloroglucinol units, neither of which binds lithium strongly, and its potential as an anode in Li-ion battery are presented. Their fibrous texture enables facile amalgamation as a coin-cell anode, which exhibits exceptionally high specific capacity of approximate to 720 mA h g(-1) (@100 mA g(-1)). Its capacity is retained even after 1000 cycles. Increasing the current density from 100 mA g(-1) to 1 A g(-1) causes the specific capacity to drop only by 20%, which is the lowest among all high-performing anodic COFs. The majority of the lithium insertion follows an ultrafast diffusion-controlled intercalation (diffusion coefficient, D-Li(+) = 5.48 x 10(-11) cm(2) s(-1)). The absence of strong Li-framework bonds in the density functional theory (DFT) optimized structure supports this reversible intercalation. The discrete monomer of the CON shows a specific capacity of only 140 mA h g(-1) @50 mA g(-1) and no sign of lithium intercalation reveals the crucial role played by the polymeric structure of the CON in this intercalation-assisted conductivity. The potentials mapped using DFT suggest a substantial electronic driving-force for the lithium intercalation. The findings underscore the potential of the designer CON as anode material for Li-ion batteries.1 aHaldar, Sattwick1 aRoy, Kingshuk1 aNandi, Shyamapada1 aChakraborty, Debanjan1 aPuthusseri, Dhanya1 aGawli, Yogesh1 aOgale, Satishchandra1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/high-and-reversible-lithium-ion-storage-self-exfoliated-triazole-triformyl-phloroglucinol02314nas a2200205 4500008004100000245014500041210006900186260000800255490000700263520153500270100002101805700002601826700001701852700001801869700002801887700002501915700001601940700003001956856012201986 2018 eng d00aHighly stable COF-supported Co/Co(OH)(2) nanoparticles heterogeneous catalyst for reduction of nitrile/nitro compounds under mild conditions0 aHighly stable COFsupported CoCoOH2 nanoparticles heterogeneous c cSEP0 v143 aOrdered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor-made properties into a COF. Here, a COF-Co/Co(OH)(2) composite containing about 16 wt% of <6 nm sized Co/Co(OH)(2) nPs is prepared on a N-rich COF support that catalyzes the release of theoretical equivalence of H-2 from readily available, safe, and cheap NaBH4. Furthermore, the released H-2 is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one-pot reaction. The COF "by choice" is built from "methoxy" functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N-rich binding pockets in the COF ensure strong nP-COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst - a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.1 aMullangi, Dinesh1 aChakraborty, Debanjan1 aPradeep, Anu1 aKoshti, Vijay1 aVinod, Chathakudath, P.1 aPanja, Soumendranath1 aNair, Sunil1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/highly-stable-cof-supported-cocooh2-nanoparticles-heterogeneous-catalyst-reduction02313nas a2200241 4500008004100000022001400041245012600055210006900181260000800250520143000258653001601688653003201704653002201736653002301758653002501781100002601806700002201832700002201854700002001876700001801896700003001914856012701944 2019 eng d a1861-472800aAg nanoparticles supported on a resorcinol-phenylenediamine-based covalent organic framework for chemical fixation of CO20 aAg nanoparticles supported on a resorcinolphenylenediaminebased  cOCT3 a

Covalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host-guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol-phenylenediamine-based COF which selectively adsorbs CO2 into its micropores (12 angstrom). The heat of adsorption value (32 kJ mol(-1)) obtained from the virial model at zero-loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small-sized Ag nanoparticles (approximate to 4-5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 %. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post-catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.

10aCO2 capture10acovalent organic frameworks10acyclic carbonates10aPropargyl alcohols10asilver nanoparticles1 aChakraborty, Debanjan1 aShekhar, Pragalbh1 aSingh, Himan, Dev1 aKushwaha, Rinku1 aVinod, C., P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/ag-nanoparticles-supported-resorcinol-phenylenediamine-based-covalent-organic-framework02516nas a2200289 4500008004100000022001400041245014300055210006900198260000800267300001400275490000600289520149400295653004001789653002001829653002001849653002001869653002801889653001901917100001701936700002601953700002201979700002402001700002102025700001802046700003002064856013202094 2019 eng d a2574-097000aAqueous-phase differentiation and speciation of Fe3+ and Fe2+ using water-stable photoluminescent lanthanide-based metal-organic framework0 aAqueousphase differentiation and speciation of Fe3 and Fe2 using cAUG a5169-51780 v23 a

Fe2+ is vital to O-2 transportation and photosynthesis regulated by oxidases and reductases. On the other hand, Fe3+ is detrimental due to its irreversible binding to O-2. Hence there is a need for selective identification of Fe3+ from aqueous systems in the presence of Fe2+. However, given their close chemical nature, it is not straightforward to differentiate them. Fe2+ and Fe3+ are typically sensed and differentiated using magnetic measurements, Mossbauer, X-ray absorption spectroscopy, or EXAFS, which are complex and equipment intensive techniques. In comparison, the fluorescence technique is advantageous in terms of time and accessibility. Although readily available lanthanide salts exhibit fluorescence, they are weak, and to serve as an optical probe, their luminescence has to be enhanced via ligand design. Hence we have designed a chromophoric ligand that can covalently bind to lanthanides and enhance its fluorescence intensity, and it binds selectively to Fe3+ through its nitrogen centers. It detects Fe3+ from low concentration (similar to 100 mu M) aqueous solutions, with fast response time (<1 min) and with a detection limit of 3.6 ppm. Importantly, the Fe3+ adsorbed MOF can be readily reactivated for the next cycle by merely washing with an aqueous ascorbic acid solution and can be used for multiple cycles without any appreciable loss in activity. This makes the Ln-MOF an environmentally benign, cost-effective, scalable, and recyclable probe.

10aFe3+ differentiation and speciation10aflexible ligand10afluorescent MOF10airon speciation10aMetal-organic framework10awater sorption1 aMaity, Rahul1 aChakraborty, Debanjan1 aNandi, Shyamapada1 aYadav, Ankit, Kumar1 aMullangi, Dinesh1 aVinod, C., P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/aqueous-phase-differentiation-and-speciation-fe3-and-fe2-using-water-stable-photoluminescent02337nas a2200253 4500008004100000022001400041245017500055210006900230260000800299300001600307490000600323520138600329100002601715700002201741700002701763700002101790700001701811700002301828700002101851700002801872700002401900700003001924856012901954 2019 eng d a2470-134300aCarbon derived from soft pyrolysis of a covalent organic framework as a support for small-sized RuO2 showing exceptionally low overpotential for oxygen evolution reaction0 aCarbon derived from soft pyrolysis of a covalent organic framewo cAUG a13465-134730 v43 a

Electrochemical water splitting is the most energy-efficient technique for producing hydrogen and oxygen, the two valuable gases. However, it is limited by the slow kinetics of the anodic oxygen evolution reaction (OER), which can be improved using catalysts. Covalent organic framework (COF)-derived porous carbon can serve as an excellent catalyst support. Here, we report high electrocatalytic activity of two composites, formed by supporting RuO2 on carbon derived from two COFs with closely related structures. These composites catalyze oxygen evolution from alkaline media with overpotentials as low as 210 and 217 mV at 10 mA/cm(2), respectively. The Tafel slopes of these catalysts (65 and 67 mV/dec) indicate fast kinetics compared to commercial RuO2. The observed activity is the highest among all RuO2-based heterogeneous OER catalysts-a touted benchmark OER catalyst. The high catalytic activity arises from the extremely small-sized (similar to 3-4 nm) RuO2 nanoparticles homogeneously dispersed in a micro-mesoporous (BET = 517 m(2)/g) COF-derived carbon. The porous graphenic carbon favors mass transfer, while its N-rich framework anchors the catalytic nanoparticles, making it highly stable and recyclable. Crucially, the soft pyrolysis of the COF enables the formation of porous carbon and simultaneous growth of small RuO2 particles without aggregation.

1 aChakraborty, Debanjan1 aNandi, Shyamapada1 aIllathvalappil, Rajith1 aMullangi, Dinesh1 aMaity, Rahul1 aSingh, Santosh, K.1 aHaldar, Sattwick1 aVinod, Chathakudath, P.1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/carbon-derived-soft-pyrolysis-covalent-organic-framework-support-small-sized-ruo2-showing02868nas a2200265 4500008004100000022001400041245015400055210006900209260000900278300001600287490000700303520188300310653002502193653003102218653003002249653002802279653002502307100002602332700002202358700002102380700002102401700002802422700003002450856012202480 2019 eng d a1944-824400aCu/Cu2O nanoparticles supported on a phenol-pyridyl COF as a heterogeneous catalyst for the synthesis of unsymmetrical diynes via glaser-hay coupling0 aCuCu2O nanoparticles supported on a phenolpyridyl COF as a heter cMAY  a15670-156790 v113 a

Covalent organic frameworks (COFs) are a new class of porous crystalline polymers with a modular construct that favors fiinctionalization. COF pores can be used to grow nanoparticles (nPs) with dramatic size reduction, stabilize them as dispersions, and provide excellent nP access. Embedding substrate binding sites in COFs can generate host-guest synergy, leading to enhanced catalytic activity. In this report, Cu/Cu2O nPs (2-3 nm) are grown on a COF, which is built by linking a phenolic trialdehyde and a triamine through Schiff bonds. Their micropores restrict the nP to exceptionally small sizes (similar to 2-3 nm), and the pore walls decorated with strategically positioned hydrogen-bonding phenolic groups anchor the substrates via hydrogen-bonding, whereas the basic pyridyl sites serve as cationic species to stabilize the [CuclusterCl2](2-) type reactive intermediates. This composite catalyst shows high activity for Glaser-Hay heterocoupling reactions, an essential 1,3-diyne yielding reaction with widespread applicability in organic synthesis and material science. Despite their broad successes in homocoupled products, preparation of unsymmetrical 1,3-diynes is challenging due to poor selectivity. Here, our COF-based Cu catalyst shows elevated selectivity toward heterocoupling product(s) (Cu nP loading 0.0992 mol %; turn over frequency: similar to 4S-50; turn over number: similar to 17S-190). The reversible redox activity at the Cu centers has been demonstrated by carrying out X-ray photoelectron spectroscopy on the frozen reactions, whereas the crucial interactions between the substrates and the binding sites in their optimized configurations have been modeled using density functional theory methods. This report emphasizes the utility of COFs in developing a heterogeneous catalyst for a truly challenging organic heterocoupling reaction.

10aCopper nanoparticles10aCovalent organic framework10aGlaser-Hay heterocoupling10aheterogeneous catalysis10aunsymmetrical diynes1 aChakraborty, Debanjan1 aNandi, Shyamapada1 aMullangi, Dinesh1 aHaldar, Sattwick1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/cucu2o-nanoparticles-supported-phenol-pyridyl-cof-heterogeneous-catalyst-synthesis02285nas a2200313 4500008004100000022001400041245011700055210006900172260000900241300001400250490000600264520120100270653002701471653003101498653002701529653002801556653001901584653001901603100002001622700002901642700002101671700002601692700002101718700001801739700002801757700002501785700003001810856013101840 2020 eng d a2574-097000aNanoporous covalent organic framework embedded with Fe/Fe3O4 nanoparticles as air-stable low-density nanomagnets0 aNanoporous covalent organic framework embedded with FeFe3O4 nano cSEP  a9088-90960 v33 a

Covalent organic frameworks (COFs) made of light atoms such as H, C, N, and O with a significant void-to-framework ratio are excellent low-density supports for nanoparticles (nPs). Their framework can be precoded with heteroatoms to ensure binding with metallic nanoclusters. With these advantages, if controlled amounts of magnetic nPs are anchored to them, they can yield low-density organic-inorganic nanomagnets. Their organic nature facilitates fusion with bulk materials such as paper/textile to enable bulk composites with well-dispersed low-density magnets, which have potential for defense and next-generation aviation applications. Herein, we have grown small Fe/Fe3O4 nPs (5-18 wt %) inside a COF. Interestingly, 300 mg of this organic-inorganic framework material (containing 50 mg of nPs) can lift a vial of similar to 15,000 mg (300 times heavier). Also, the hydrophobic COF wraps around the Fe/Fe3O4 nanocluster retaining its room-temperature magnetic character even after 1 year, while the naked nPs lose it within a few days because of air oxidation. Bulk composites with paper and polymers have been made using this low-density Fe-COF to demonstrate their processability.

10aair-stable nanomagnets10aCovalent organic framework10aFe/Fe3O4 nanoparticles10alow-density nanomagnets10amagnetic rayon10ananoporous COF1 aKushwaha, Rinku1 aKaleeswaran, Dhananjayan1 aHaldar, Sattwick1 aChakraborty, Debanjan1 aMullangi, Dinesh1 aBorah, Aditya1 aVinod, Chathakudath, P.1 aMurugavel, Ramaswamy1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/nanoporous-covalent-organic-framework-embedded-fefe3o4-nanoparticles-air-stable-low-density02395nas a2200301 4500008004100000022001400041245013200055210006900187260000800256300001200264490000800276520136300284653001501647653002201662653001901684653003401703653003401737653002901771100001801800700001801818700001801836700001901854700001901873700001401892700003001906700002501936856013201961 2020 eng d a0008-622300aRoom temperature processed in-situ carbon-coated vanadium carbide (VC@C) as a high capacity robust Li/Na battery anode material0 aRoom temperature processed insitu carboncoated vanadium carbide  cMAY a108-1160 v1613 a

3D carbide systems with their robust physical and mechanical properties have always attracted multiple application interests. In this report, we have synthesized a three-dimensional in-situ carbon coated cubic carbide, Vanadium Carbide (VC@C), by a very simple, scalable and cost-effective room temperature mechano-chemical ball-milling procedure and researched its promise as effective anode material for Li and Na ion batteries. We have demonstrated that VC@C shows an impressive initial discharge/lithiation capacity of 1165 mAh g(-1) with a high reversible capacity of 640 mAh g(-1) after 100 charge-discharge cycles at an applied current density of 0.1 A g(-1). We have also found that this material renders a very promising rate performance with significantly low capacity drop after exposing it to variable current densities ranging from 0.05 A g(-1) to 2 A g(-1) with an excellent stability up to 1000 cycles owing to its structural robustness, as verified by post-cycling characterizations. A Li-ion full cell study using LiCoO2 as cathode also showed excellent promise in terms of practical application demonstrating a reversible capacity of 95 mAh g(-1) after 100 cycles. Even for Na insertion/de-insertion VC@C shows a clear promise in terms of capacity, cyclic stability and rate performance. (C) 2020 Elsevier Ltd. All rights reserved.

10a3D carbide10aIn-situ synthesis10aLi-ion battery10aPost cycling characterization10aRoom temperature ball milling10aWilliamson-Hall analysis1 aMahajan, Mani1 aRoy, Kingshuk1 aParmar, Swati1 aSingla, Gourav1 aPandey, O., P.1 aSingh, K.1 aVaidhyanathan, Ramanathan1 aOgale, Satishchandra uhttps://library.ncl.res.in/content/room-temperature-processed-situ-carbon-coated-vanadium-carbide-vcc-high-capacity-robust-lina02575nas a2200313 4500008004100000022001400041245013000055210006900185260000800254300001200262490000700274520150800281653003201789653001501821653002301836653001701859653002101876653002001897100002001917700002101937700002201958700002201980700001802002700001702020700003602037700003002073700003002103856012802133 2021 eng d a1614-683200aExceptional capacitance enhancement of a non-conducting COF through potential-driven chemical modulation by redox electrolyte0 aExceptional capacitance enhancement of a nonconducting COF throu cAPR a20036260 v113 a

Capacitors are the most practical high-storage and rapid charge-release devices. The number of ions stored per unit area and their interaction strength with the electrode dictates capacitor-performance. Microporous materials provide a high storage surface and optimal interactions. Adsorbing electron-rich and easily polarizable molecules into microporous electrodes is expected to boost Faradaic pseudo-activity. If such electrode-electrolyte interactions can be made as a potential-driven reversible process, the resulting capacitors would be adaptable and device-friendly. A composite covalent organic framework (COF)-carbon electrode with redox-active KI is combined in an H2SO4 electrolyte for the first time. This composite electrode benefits from the redox-functionality of COF and electronic conductivity of carbon, leading to superior capacitative activity. Operando spectro-electrochemical measurements reveal the existence of multiple polyiodide species, although the I-3(-) is the predominantly electroactive species adsorbing on the microporous triazine-phenol COF electrode. A systematic fabrication of the flexible solid-state devices using the COF-redox-electrolyte reveals a high areal capacitance of 270 +/- 11 mF cm(-2) and gravimetric capacitance of 57 +/- 8 F g(-1). The inclusion of KI in H2SO4 (electrolyte) yields an approximately eight-fold enhancement in solid-state gravimetric specific capacitance. The imine-COF retains 89% of its capacity even after 10 000 cycles.

10acovalent organic frameworks10apolyiodide10aredox electrolytes10asolid&\#820810astate capacitors10aSupercapacitors1 aKushwaha, Rinku1 aHaldar, Sattwick1 aShekhar, Pragalbh1 aKrishnan, Akshara1 aSaha, Jayeeta1 aHui, Pramiti1 aVinod, Chathakudath, Prabhakara1 aSubramaniam, Chandramouli1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/exceptional-capacitance-enhancement-non-conducting-cof-through-potential-driven-chemical01233nas a2200217 4500008004100000022001400041245012600055210006900181260000900250300001600259490000700275520044400282100002300726700001700749700002300766700001900789700001900808700003000827700002800857856013000885 2021 eng d a0022-326300aThree in one: triple G-C-T base-coded brahma nucleobase amino acid: synthesis, peptide formation, and structural features0 aThree in one triple GCT basecoded brahma nucleobase amino acid s cNOV  a15689-156940 v863 aThis note reports the synthesis and peptide formation of a novel triple G-C-T nucleobase amino acid (NBA) building block featuring three recognition faces: DDA (G mimic), DAA (C mimic), and ADA (T mimic). Readily obtainable in multigram scale in a remarkably easy one-step reaction, this unique NBA building block offers scope for wide ranging applications for nucleic acid recognition and nucleic acid peptide/protein interaction studies.1 aWagh, Mahendra, A.1 aMaity, Rahul1 aBhosale, Rohit, J.1 aSemwal, Divyam1 aTothadi, Srinu1 aVaidhyanathan, Ramanathan1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/three-one-triple-g-c-t-base-coded-brahma-nucleobase-amino-acid-synthesis-peptide-formation02165nas a2200253 4500008004100000022001400041245008400055210006900139260000800208300001500216490000700231520135000238653001601588653001701604653001101621653001701632100002201649700002201671700002601693700002101719700002801740700003001768856011301798 2022 eng d a1861-472800aCoordination flexibility aided CO2-specific gating in an iron isonicotinate MOF0 aCoordination flexibility aided CO2specific gating in an iron iso cFEB ae2021013050 v173 a

Coordination flexibility assisted porosity has been introduced into an Iron-isonicotinate metal-organic framework (MOF), (Fe(4-PyC)(2) . (OH). The framework showed CO2-specific gate opening behavior, which gets tuned as a function of temperature and pressure. The MOF ` s physisorptive porosity towards CO2, CH4, and N-2 was investigated; it adsorbed only CO2 via a gate opening phenomenon. The isonicotinate, representing a borderline soft base, is bound to the hard Fe3+ centre through monodentate carboxylate and pyridyl nitrogen. This moderately weak binding enables isonicotinate to spin like a spindle under the CO2 pressure opening the gate for a sharp increase in CO2 uptake at 333 mmHg (At 298 K, the CO2 uptake increases from 0.70 to 1.57 mmol/g). We investigated the MOF ` s potential for CO2/N-2 and CO2/CH4 gas separation aided by this gating. IAST model reveals that the CO2/N-2 selectivity jumps from 325 to 3131 when the gate opens, while the CO2/CH4 selectivity increases three times. Interestingly, this Fe-isonicotinate MOF did not follow the trend set by our earlier reported Hard-Soft Gate Control (established for isostructural M2+-isonicotinate MOFs (M=Mg, Mn)). However, we account for this discrepancy using the different oxidation state of metals confirmed by X-ray photoelectron spectroscopy and magnetism.

10aCO2 capture10aflexible MOF10agating10aIsonicotinic1 aSingh, Himan, Dev1 aNandi, Shyamapada1 aChakraborty, Debanjan1 aSingh, Kirandeep1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/coordination-flexibility-aided-co2-specific-gating-iron-isonicotinate-mof02813nas a2200229 4500008004100000022001400041245013100055210006900186260000800255300001600263490000700279520198000286100002302266700002202289700001802311700002202329700001702351700002602368700002802394700003002422856013102452 2022 eng d a2050-748800aCovalent organic framework with electrodeposited copper nanoparticles - a desirable catalyst for the Ullmann coupling reaction0 aCovalent organic framework with electrodeposited copper nanopart cJUL a15647-156560 v103 a

A covalent organic framework is a porous covalently-linked polymeric assembly built from molecular lego blocks, the monomers. A COF's high surface area, ordered pores, and intrinsic low density makes it a perfect heterogeneous catalyst component. Dispersing catalytic metal nanoparticles into the porous COF matrix in a `capping-agent-free' manner can aid the maximal utilization of the active sites. To generate single-site catalysts, metals have been anchored to dense supports, or metal ions have been coordinated to the porous organic framework. The latter has superior atom efficiency and a substrate diffusion advantage. Stably nestling neutral metallic clusters into open-framework supports with no specifically strong binding groups requires a different approach. If infused from extremely dilute electrolytes, metal clusters can be nanoconfined into electrically activated COFs. At low-loadings, it can resemble a single-site catalyst with high atom efficiency. Herein, we report the larger scale synthesis of IISERP-COF15 and electrochemical loading of copper nanoparticles into its pores at loadings as low as 3.34 wt%. We employed classical Ullmann reactions to adjudge its activity. Typical turnover numbers for the catalysts reported in the literature are approximately 50-100. A Cu@COF shows high activity with a very low catalyst loading of 0.25 mol% (TON around similar to 300-350 vs. 4 for neat CuCl2 center dot 2H(2)O (homogeneous catalyst) and turnover frequency (similar to 15-17 h(-1))). We recycled it for up to 3 cycles. Furthermore, we report a multi-fold Ullmann reaction producing an unreported hexaaldehyde to demonstrate the latitude of the catalyst. Our work points to the potential of a dilutely loaded metal@COF as a mimic of the single-site catalyst for synthesizing valuable C-O linked molecules. Our findings from computational modeling shed light on the role of the COF as an active nanoporous support for Ullmann C-O coupling.

1 aChandran, Chandana1 aSingh, Himan, Dev1 aLeo, Liya, S.1 aShekhar, Pragalbh1 aRase, Deepak1 aChakraborty, Debanjan1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/covalent-organic-framework-electrodeposited-copper-nanoparticles-desirable-catalyst-ullmann02525nas a2200301 4500008004100000022001400041245011100055210006900166260000800235300001200243490000700255520151500262653002701777653002801804653001701832653002701849653002701876100002101903700001701924700002201941700001801963700003601981700001402017700002302031700001902054700003002073856012002103 2022 eng d a1614-683200aIncorporating conducting polypyrrole into a polyimide COF for carbon-free ultra-high energy supercapacitor0 aIncorporating conducting polypyrrole into a polyimide COF for ca cSEP a22007540 v123 a

Redox-active covalent organic frameworks (COFs) store charges but possess inadequate electronic conductivity. Their capacitive action works by storing H+ ions in an acidic electrolyte and is typically confined to a small voltage window (0-1 V). Increasing this window means higher energy and power density, but this risks COF stability. Advantageously, COF's large pores allow the storage of polarizable bulky ions under a wider voltage thus reaching higher energy density. Here, a COF-electrode-electrolyte system operating at a high voltage regime without any conducting carbon or redox active oxides is presented. Conducting polypyrrole (Ppy) chains are synthesized within a polyimide COF to gain electronic conductivity (approximate to 10 000-fold). A carbon-free quasi-solid-state capacitor assembled using this composite showcases high pseudo-capacitance (358 mF cm(-2)@1 mA cm(-2)) in an aqueous gel electrolyte. The synergy among the redox-active polyimide COF, polypyrrole and organic electrolytes allows a wide-voltage window (0-2.5 V) leading to high energy (145 mu Wh cm(-2)) and power densities (4509 mu W cm(-2)). Amalgamating the polyimide-COF and the polypyrrole as one material minimizes the charge and mass transport resistances. Computation and experiments reveal that even a partial translation of the modules/monomers intrinsic electronics to the COF imparts excellent electrochemical activity. The findings unveil COF-confined polymers as carbon-free energy storage materials.

10acarbon free capacitors10acation-anion co-storage10aconductivity10ahigh energy capacitors10apolypyrrole doped COFs1 aHaldar, Sattwick1 aRase, Deepak1 aShekhar, Pragalbh1 aJain, Chitvan1 aVinod, Chathakudath, Prabhakara1 aZhang, En1 aShupletsov, Leonid1 aKaskel, Stefan1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/incorporating-conducting-polypyrrole-polyimide-cof-carbon-free-ultra-high-energy02844nas a2200301 4500008004100000245017400041210006900215260000900284300001400293490000600307520174100313653001202054653001402066653003102080653002802111653001802139653002402157100003702181700002002218700001802238700002202256700002202278700002602300700003602326700003002362700001802392856013202410 2022 eng d00aSynergistic electronic effects in AuCo nanoparticles stabilized in a triazine-based covalent organic framework: a catalyst for methyl orange and methylene blue reduction0 aSynergistic electronic effects in AuCo nanoparticles stabilized  cAPR  a4744-47530 v53 a

Developing stable active catalysts for reducing water-soluble pollutants is a desirable target. In this pursuit, we have functionalized covalent organic frameworks (COFs) with gold (Au) and cobalt (Co) nanoparticles via a one-step aqueous synthesis process, and their catalytic activity in reducing methyl orange and methylene blue is examined. Operando absorbance measurements of methyl orange (anionic dye) reduction revealed AuCoCOF (1.3 Au/1.0 Co) to have superior kinetics over many other catalysts, which typically require additional external stimuli (e.g., photons) and higher catalyst loadings. After confirming the homogeneous dispersion of the nanoparticles on the COF support using three-dimensional (3D) tomography and material stability through powder X-ray diffraction (PXRD), infrared (IR), and thermal studies, we investigated their redox activity. Cyclic voltammetry (CV) confirmed the involvement of both metals in the redox process, while spectroelectrochemical measurements show that their activity and kinetics remain unaltered by an applied potential. Solid-state UV measurements reveal that the neat COF is a semiconductor with a large band gap (2.8 eV), which is substantially lowered when loaded with cobalt nanoparticles (2.2 eV for CoCOF). The electronic synergy between Au and Co nanoparticles further reduces the band gap of AuCoCOF (1.9 eV). Thus, there is a definite advantage in doping non-noble metal nanoparticles into a noble metal lattice and nanoconfining them into a porous COF support. Our study highlights the significance of bimetallic COF-supported nanocatalysts, wherein one can engage each component toward targeted applications that demand redox activity with favorable kinetics.

10aAuCoCOF10aband gaps10aCovalent organic framework10amethyl orange reduction10aNanoparticles10aUV-vis spectroscopy1 aDevulapalli, Venkata, Swaroopa D1 aKushwaha, Rinku1 aOvalle, Edwin1 aSingh, Himan, Dev1 aShekhar, Pragalbh1 aChakraborty, Debanjan1 aVinod, Chathakudath, Prabhakara1 aVaidhyanathan, Ramanathan1 aBorguet, Eric uhttps://library.ncl.res.in/content/synergistic-electronic-effects-auco-nanoparticles-stabilized-triazine-based-covalent-organic02092nas a2200277 4500008004100000245013500041210006900176260000800245300001100253490000700264520112600271100002201397700003701419700001701456700002201473700001701495700001801512700001701530700002701547700002501574700002001599700002601619700001801645700003001663856012101693 2023 eng d00aCOF-supported zirconium oxyhydroxide as a versatile heterogeneous catalyst for Knoevenagel condensation and nerve agent hydrolysis0 aCOFsupported zirconium oxyhydroxide as a versatile heterogeneous cNOV a1080880 v263 a

A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt %) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF's structure is pre-served after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distri-bution of nano-to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrOx(OH)(y)@COF's nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol % of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h(-1) for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol % of catalyst catalyzes the hy-drolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37% in 180 min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrOx(OH)(y) as a new class of zirconium-based Lewis + Bronsted-acid catalysts.

1 aShekhar, Pragalbh1 aDevulapalli, Venkata, Swaroopa D1 aReji, Reshma1 aSingh, Himan, Dev1 aJose, Aleena1 aSingh, Piyush1 aTorris, Arun1 aVinod, Chatakudath, P.1 aIII, John, A. Tokarz1 aMahle, John, J.1 aPeterson, Gregory, W.1 aBorguet, Eric1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/cof-supported-zirconium-oxyhydroxide-versatile-heterogeneous-catalyst-knoevenagel03138nas a2200253 4500008004100000022001400041245012100055210006900176260000900245300001200254490000600266520224700272100001702519700002702536700002202563700002202585700001802607700002602625700002102651700001902672700003202691700003002723856013102753 2023 eng d a2055-675600aHydroxide ion-conducting viologen-bakelite organic frameworks for flexible solid-state zinc-air battery applications0 aHydroxide ionconducting viologenbakelite organic frameworks for  cJAN  a224-2340 v83 a

Adaptable polymer-based solid-state electrolytes can be a game-changer toward safe, lightweight flexible batteries. We present a robust Bakelite-type organic polymer covalently decked with viologen, triazine, and phenolic moieties. Its flexible structure with cationic viologen centers incorporates counter-balancing free hydroxide ions into the polymeric framework. By design, the aromatic groups and heteroatoms in the framework can be activated under an applied potential to prompt a push-pull drive, setting off the towing of hydroxide ions via weak electrostatic, van der Waals, and hydrogen-bond interactions. The frontier orbitals from a DFT-modeled structure certify this. The hydroxyl-polymer requires minimal KOH wetting to maintain a humid environment for Grotthuss-type transport. The hydroxide ion conductivity reaches a value of 1.4 x 10(-2) S cm(-1) at 80 degrees C and 95% RH, which is retained for over 15 h. We enhanced its practical utility by coating it as a thin solid-state separator-cum-electrolyte on readily available filter paper. The composite exhibits a conductivity of 4.5 x 10(-3) S cm(-1) at 80 degrees C and 95% RH. A zinc-air battery (ZAB) constructed using this polymer-coated paper as electrolyte yields a maximum power density of 115 mW cm(-2) and high specific capacitance of 435 mA h g(-1). The power density recorded for our ZAB is among the best reported for polymer electrolyte-based batteries. Subsequently, the flexible battery fabricated with IISERP-POF11_OH@FilterPaper exhibits an OCV of 1.44 V, and three batteries in series power a demo traffic signal. To underscore the efficiency of hydroxide ion transport through the complex multifunctional backbone of the polymer, we calculated the diffusion coefficient for OH- (Exp: 2.9 x 10(-5) cm(2) s(-1); Comp. 5.2 x 10(-6) cm(2) s(-1)) using electrochemical methods and MD simulations. Climbing-edge NEB calculations reveal a large energy barrier of 2.11 eV for Zn2+ to penetrate the polymer and identify hydroxide ions within the polymer, suggesting no undesirable Zn2+ crossover. Our findings assert the readily accessible C-C-linked cationic polymer's capacity as a solid-state electrolyte for ZABs and any anion-conducting membrane.

1 aRase, Deepak1 aIllathvalappil, Rajith1 aSingh, Himan, Dev1 aShekhar, Pragalbh1 aLeo, Liya, S.1 aChakraborty, Debanjan1 aHaldar, Sattwick1 aShelke, Ankita1 aAjithkumar, Thalasseril, G.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/hydroxide-ion-conducting-viologen-bakelite-organic-frameworks-flexible-solid-state-zinc-air02409nas a2200289 4500008004100000022001400041245011300055210006900168260000800237490000700245520141200252653003201664653002301696653001501719653002301734653002101757100002001778700001801798700002201816700001701838700002701855700001601882700002301898700003601921700003001957856013201987 2023 eng d a1614-683200aMade to measure squaramide COF cathode for zinc dual-ion battery with enriched storage via redox electrolyte0 aMade to measure squaramide COF cathode for zinc dualion battery  cSEP0 v133 a

Aqueous rechargeable batteries are promising grid-scale energy storage devices because of their affordability, operational safety, and environmental benignity. Among these, Zn-ion batteries (ZIBs) have unfolded new horizons. Designing superior cathodes for ZIBs is crucial. Covalent organic frameworks (COFs) can be made redox active with a high storage surface. Here, for the first time, a chelating COF with redox-active ZnI2 in a ZnSO4(aq) electrolyte is combined. Including iodide harvests an approximately threefold enhancement in capacity from 208 to 690 mAh g(-1) at 1.5 A g(-1), the highest among all the COF-derived ZIBs. Remarkably, a charge-discharge curve at 1.3 V exhibits very limited dropout voltage and super-flat platform, with a remarkable capacity of 600 mAh g(-1) at 5 A g(-1) stable up to 6000 cycles, confirming that the polyiodide generation and storage are sustainable. The COF's dual-ion storage (Zn2+ and polyidode) delivers a ZIB with the highest energy density. Spectro-electrochemical measurements coupled with X-ray photoelectron spectroscopy unambiguously unveil the existence of multiple polyiodide species, with I-3(-) and IO3- ions as the prominent species. The latter gets reduced at the COF electrode under an applied potential, leaving I-3(-) as the major species stored on the COF. The prospect of COF-polyiodide((aq)) is a windfall for metal-ion batteries.

10acovalent organic frameworks10aflexible batteries10apolyiodide10aredox electrolytes10aZn ion batteries1 aKushwaha, Rinku1 aJain, Chitvan1 aShekhar, Pragalbh1 aRase, Deepak1 aIllathvalappil, Rajith1 aMekan, Deep1 aCamellus, Augastus1 aVinod, Chathakudath, Prabhakara1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/made-measure-squaramide-cof-cathode-zinc-dual-ion-battery-enriched-storage-redox-electrolyte02348nas a2200265 4500008004100000022001400041245014300055210006900198260000800267300001200275490000800287520138500295653003201680653002801712100001801740700002001758700001701778700002201795700001901817700001901836700003201855700003601887700003001923856012901953 2023 eng d a0002-786300aTailoring COFs: transforming nonconducting 2D layered COF into a conducting quasi-3D architecture via interlayer knitting with polypyrrole0 aTailoring COFs transforming nonconducting 2D layered COF into a  cDEC a487-4990 v1463 a

Improving the electronic conductivity and the structural robustness of covalent organic frameworks (COFs) is paramount. Here, we covalently cross-link a 2D COF with polypyrrole (Ppy) chains to form a quasi-3D COF. The 3D COF shows well-defined reflections in the SAED patterns distinctly indexed to its modeled crystal structure. This knitting of 2D COF layers with conjugated polypyrrole units improves electronic conductivity from 10(-9) to 10(-2 )S m(-1). This conductivity boost is affirmed by the presence of density of states near the Fermi level in the 3D COF, and this elevates the COF's valence band maximum by 0.52 eV with respect to the parent 2D pyrrole-functionalized COF, which agrees well with the opto-electro band gaps. The extent of HOMO elevation suggests the predominant existence of a polaron state (radical cation), giving rise to a strong EPR signal, most likely sourced from the cross-linking polypyrrole chains. A supercapacitor devised with COF20-Ppy records a high areal capacitance of 377.6 mF cm(-2), higher than that of the COF loaded with noncovalently linked polypyrrole chains. Thus, the polypyrrole acts as a ``conjugation bridge'' across the layers, lowering the band gap and providing polarons and additional conduction pathways. This marks a far-reaching approach to converting many 2D COFs into highly ordered and conducting 3D ones.

10acovalent organic frameworks10aElectrical conductivity1 aJain, Chitvan1 aKushwaha, Rinku1 aRase, Deepak1 aShekhar, Pragalbh1 aShelke, Ankita1 aSonwani, Disha1 aAjithkumar, Thalasseril, G.1 aVinod, Chathakudath, Prabhakara1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/tailoring-cofs-transforming-nonconducting-2d-layered-cof-conducting-quasi-3d-architecture01101nas a2200325 4500008004100000022001400041245015200055210006900207260000800276300001400284490000700298653001500305653001300320653002000333653001400353100002200367700001800389700002200407700002000429700001700449700002200466700001800488700001800506700001900524700003600543700001500579700002300594700003000617856012800647 2024 eng d a0897-475600aResorcinol-Azodianiline Covalent Organic Framework Supported FeOOH Quantum Dot-Catalyzed Electrochemical Ammonia Synthesis under Ambient Conditions0 aResorcinolAzodianiline Covalent Organic Framework Supported FeOO cAUG a8229-82380 v3610aconversion10anitrogen10aRecent Progress10areduction1 aShekhar, Pragalbh1 aKosugi, Kento1 aSingh, Himan, Dev1 aKushwaha, Rinku1 aRase, Deepak1 aMatsuzaki, Takumi1 aJain, Chitvan1 aSingh, Piyush1 aSingh, Yashraj1 aVinod, Chathakudath, Prabhakara1 aKondo, Mio1 aMasaoka, Shigeyuki1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/resorcinol-azodianiline-covalent-organic-framework-supported-feooh-quantum-dot-catalyzed