01879nas a2200253 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520105200266653001601318653001101334653002701345653000801372653001401380653001901394653001401413100002901427700001101456700002601467856013201493 2021 eng d a0169-433200aSubstrate augmented catalytic activity towards NRR: a case study of Li doped Al clusters on defective graphene0 aSubstrate augmented catalytic activity towards NRR a case study  cNOV a1505860 v5663 aDensity Functional Theory (DFT) based methods are applied to examine the potential of lithium doped aluminium clusters consisting of 3-13 atoms for dinitmgen molecule activation in terms of N N bond length, redshift in N N bond stretching frequency, nitrogen interaction energy and frontier molecular orbitals analysis. The present work highlights the role of monovacant C-3 defective graphene as a support in fine tuning the catalytic activity of Li doped Al clusters for reduction of N-2. Fundamental insights to synergic binding of clusters with defective graphene is brought out and its role in enhancing activation of dinitmgen molecule is explained. Supported Aln-1Li clusters with six or more atoms are noted to be more active towards N-2 molecule activation as compared to the clusters without support. Dinitrogen molecule undergoes a maximum bond elongation of 1.56 angstrom corresponding to redshift of 1690 cm(-1) on Al7Li@graphene and Al12Li@graphene. This is maximum value reported in context of activation for N-2 molecule till date.10aAl clusters10aAl12Li10aC-3 defective graphene10aDFT10aLi Doping10aN-2 activation10aRed-shift1 aSamal, Pragnya, Paramita1 aPoonam1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/substrate-augmented-catalytic-activity-towards-nrr-case-study-li-doped-al-clusters-defective01988nas a2200217 4500008004100000022001400041245017200055210006900227260000900296300001600305490000700321520113700328100002901465700002901494700002601523700002401549700002201573700001501595700002901610856013101639 2023 eng d a0743-746300aSulfonated zinc phthalocyanine coating as an efficient and ecofriendly corrosion inhibitor for copper surfaces: an in silico led design and its experimental validation0 aSulfonated zinc phthalocyanine coating as an efficient and ecofr cNOV  a17295-173070 v393 a

The current study highlights the successful integration of an in silico design with experimental validation to create a highly effective corrosion inhibitor for copper (Cu) surfaces. The synthesized sulfonated zinc phthalocyanine (Zn-Pc) is electrochemically characterized and demonstrates an impressive 97% inhibition efficiency, comparable to the widely used industrial corrosion inhibitor, BTA, for Cu surfaces. The corrosion inhibition is comprehensively analyzed through potentiodynamic polarization and impedance spectroscopy techniques, supported by their respective equivalent circuits. Furthermore, the sample undergoes thorough characterization using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, contact angle measurements, and atomic force microscopy. Density functional theory calculations reveal that sulfonated Zn-Pc exhibits the highest interaction energy, underscoring its exceptional inhibition properties. These results open possibilities for utilizing computational methods to design and optimize corrosion inhibitors for protection of Cu surfaces.

1 aDekshinamoorthy, Amuthan1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aKhatri, Praveen, K.1 aJain, Suman, Lata1 aRay, Anjan1 aVijayaraghavan, Saranyan uhttps://library.ncl.res.in/content/sulfonated-zinc-phthalocyanine-coating-efficient-and-ecofriendly-corrosion-inhibitor-copper03587nas a2200181 4500008004100000245015100041210006900192260000800261300001600269490000600285520287600291100001603167700001803183700002903201700002603230700002003256856012903276 2024 eng d00aSynergistic combination of ZnCl2/Cu-BTC MOF for the photocatalytic oxidative deamination of benzylamines using CO2 under visible-light irradiation0 aSynergistic combination of ZnCl2CuBTC MOF for the photocatalytic cJUL a2095–21010 v23 a

This paper demonstrates the first CO2-mediated oxidative deamination of benzylamines to benzaldehydes using a combination of ZnCl2 and Cu-BTC MOF as photocatalysts in a carbon tetrachloride solvent under visible-light irradiation. Interestingly, the synergistic combination of ZnCl2 and Cu-BTC afforded the targeted oxidation of benzylamine to benzaldehyde, wherein CO2 acted as an oxidant. The individual components yielded the corresponding imine as the main product, resulting from the oxidative coupling of the benzylamine. DFT calculations and computational studies supported the proposed reaction pathways involving the formation of an intermediate imine from benzylamine via dehydrogenation followed by hydrolysis to produce benzaldehyde. This work, demonstrating the use of CO2 as an oxidant, may open up new avenues for CO2 utilization in chemical production by using sustainable light energy.

1 aKumar, Amod1 aBhatt, Sakshi1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aJain, Suman, L. uhttps://library.ncl.res.in/content/synergistic-combination-zncl2cu-btc-mof-photocatalytic-oxidative-deamination-benzylamines02238nas a2200193 4500008004100000022001400041245013300055210006900188260000800257300001400265490000700279520150900286100002201795700002001817700002901837700002601866700002001892856013201912 2025 eng d a2044-475300asyn-Selective hydrosilylation and hydroboration of alkynes at room temperature catalyzed by a phosphine-free (NNN)Fe(ii) complex0 asynSelective hydrosilylation and hydroboration of alkynes at roo cNOV a6716-67250 v153 a

Catalytic hydrofunctionalization of alkynes is the ideal and atom-economical route to synthesize vinylsilanes and vinylboronates, which are valuable organic building blocks. However, the process suffers from using expensive phosphine-ligated catalysts, sensitive organometallic activators, and elevated reaction temperatures. To overcome these challenges, herein, we developed a series of phosphine-free (NNN)-ligated iron complexes and demonstrated their potential as efficient catalysts for the hydrosilylation and hydroboration of both internal and terminal alkynes using NaOtBu as an activator. The reactions proceeded smoothly using 1.5 mol% catalyst loading at room temperature and provided syn-selective vinylsilanes and vinylboronates. This hydrofunctionalization exclusively delivered mono-silylated and mono-borylated vinyls with tolerance of sensitive functionalities. At the same time, terminal alkynes provided excellent anti-Markovnikov selectivity with thermodynamically feasible beta-(E)-vinylsilanes and beta-(E)-vinylboronates. The presence of an N-H moiety in the ligand backbone is crucial in generating an Fe(ii) active catalyst and facilitating the catalytic process. Mechanistic investigations, including controlled reactions and external additive experiments, were performed to propose a redox-neutral reaction mechanism with iron maintaining its +2 oxidation state throughout the cycle. The DFT energy calculations unanimously support the proposed reaction mechanism.

1 aPradhan, Chandini1 aDubey, Shivansh1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aPunji, Benudhar uhttps://library.ncl.res.in/content/syn-selective-hydrosilylation-and-hydroboration-alkynes-room-temperature-catalyzed-phosphine