00989nas 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-oxidation02149nas 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-phloroglucinol02516nas 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-synthesis02165nas 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-mof