01191nas a2200229 4500008004100000022001400041245014500055210006900200260000800269520029900277653003800576653002900614653000800643653003300651653003400684100002500718700002100743700002000764700002300784700002500807856012900832 2020 eng d a0739-110200aEvaluation of biomolecular interactions and cytotoxic activity of organometallic binuclear Ru(II) complexes of ferrocenyl thiosemicarbazones0 aEvaluation of biomolecular interactions and cytotoxic activity o cJUL3 a

{Four new ferrocenyl substituted thiosemicarbazone ligands (L1-L4) and their corresponding binuclear ruthenium(II) arene complexes of the general type [(eta(6)-pcym)(L)Ru(mu-im)Ru(L)(eta(6)-p-cym)]Cl (C1-C4) and [(eta(6)-pcym)(L)Ru(mu-azpy)Ru(L)(eta(6)-p-cym)]Cl-2(C5-C8) (cym = cymene

10abinuclear ruthenium(II) complexes10aBSA binding interactions10aDNA10aFerrocenyl thiosemicarbazone10aHeLa human cervical carcinoma1 aKhanvilkar, Priyanka1 aDash, Soumya, R.1 aVohra, Alisagar1 aDevkar, Ranjitsinh1 aChakraborty, Debjani uhttps://library.ncl.res.in/content/evaluation-biomolecular-interactions-and-cytotoxic-activity-organometallic-binuclear-ruii02096nas a2200265 4500008004100000022001400041245015300055210006900208260000800277490000700285520111600292653003901408653002901447653002101476653000801497653002701505653003401532100002501566700002101591700002301612700002101635700002301656700002501679856012601704 2021 eng d a1735-207X00aImidazole/4,4 `-azopyridine bridging binuclear Ru(II) complexes: design, synthesis, bimolecular interactions and cytotoxicity against HeLa cell line0 aImidazole44 azopyridine bridging binuclear RuII complexes design cDEC0 v183 a

Binuclear Ru(II)-arene complexes [(eta(6)-pcym)(Flq)Ru(mu-im/mu-azpy)Ru(Flq)(eta(6)-p-cym)]Cl (C1-C8) (cym = cymene; Flq = fluoroquinolones; im = imidazole; azpy = 4,4 ` azo pyridine) have been synthesized and characterized by elemental analysis, molar conductivity and various spectral techniques (ESI-MS, IR, UV-Vis and H-1-NMR). The geometry of the complexes was optimized by DFT calculations, which revealed a pseudo-octahedral coordination around each metal centre. Binding of the synthesized complexes with CT-DNA and BSA was studied spectroscopically, and it has been established that the presence of two hydrophobic planar arene moieties enhances the binding efficacies of the binuclear complexes to the macromolecules, compared to their mononuclear analogues. The results of competitive binding between C1-C8 and ethidium bromide (EB) towards DNA have shown that the complexes are able to displace EB from DNA-EB adduct and interact with DNA via intercalation. The complexes display cytotoxicity against the HeLa human cervical cancer cell lines with IC50 values in the range of 30.1-120.9 mu M.

10aBinuclear ruthenium (II) complexes10aBSA binding interactions10aDFT calculations10aDNA10aFluoroquinolones (FQs)10aHeLa human cervical carcinoma1 aKhanvilkar, Priyanka1 aDash, Soumya, R.1 aPulipaka, Ramadevi1 aShirsath, Kavita1 aDevkar, Ranjitsinh1 aChakraborty, Debjani uhttps://library.ncl.res.in/content/imidazole44-azopyridine-bridging-binuclear-ruii-complexes-design-synthesis-bimolecular02563nas a2200265 4500008004100000022001400041245016500055210006900220260000800289300001000297490000700307520156800314653003901882653002901921653000801950653003401958653003901992100002502031700002102056700002202077700002002099700002302119700002502142856013002167 2021 eng d a0268-260500aOrganoruthenium (II) complexes featuring pyrazole-linked thiosemicarbazone ligands: synthesis, DNA/BSA interactions, molecular docking, and cytotoxicity studies0 aOrganoruthenium II complexes featuring pyrazolelinked thiosemica cOCT ae63430 v353 aA series of pyrazol-derived thiosemicarbazone ligands (L1-L4) were synthesized and reacted with [Ru(p-cymene)(mu-Cl)Cl](2) to yield a series of ``piano-stool''-type binuclear ruthenium (II)-arene-thiosemicarbazone complexes (C1-C8) of the general type [(Ru(eta(6)-p-cym)L)(2)(mu-im/azpy)] Cl1-2 (L = diphenylpyrazole thiosemicarbazone; cym = p-cymene; im = imidazole; azpy = 4,4 `-azopyridine). The thiosemicarbazone ligands act as N and S donors binding to the Ru(II) center via the imine nitrogen and the thione sulfur atoms. The complexes were characterized by NMR, FTIR, UV-Vis spectroscopy, and ESI+ mass spectrometry. The binding of the complexes to calf thymus deoxyribonucleic acid (CT-DNA) and bovine serum albumin (BSA) was evaluated, and it has been established that the binuclear complexes have good binding efficacies with DNA (K-b = 10(4)-10(5) M-1) and BSA (K-a = 10(5)-10(6) M-1). This is attributed to the arene moieties present in the ligands of the complexes that can have hydrophobic interactions with DNA/BSA. Ethidium bromide (EB) displacement studies and DNA viscosity measurements revealed intercalative interaction of the complexes with DNA. Static interaction of the complexes with BSA was revealed by fluorescence quenching studies. Molecular docking studies confirmed base stacking, H-bonding, and hydrophobic interactions with the biomolecules. In vitro antiproliferative studies of the complexes affirmed that the complexes are cytotoxic towards the HeLa (human cervical cancer) cell line with IC50 values in range of 17.3-41.3 mu M.10aBinuclear ruthenium (II) complexes10aBSA binding interactions10aDNA10aHeLa human cervical carcinoma10apyrazole-derived thiosemicarbazone1 aKhanvilkar, Priyanka1 aDash, Soumya, R.1 aBanerjee, Devjani1 aVohra, Aliasgar1 aDevkar, Ranjitsinh1 aChakraborty, Debjani uhttps://library.ncl.res.in/content/organoruthenium-ii-complexes-featuring-pyrazole-linked-thiosemicarbazone-ligands-synthesis02512nas a2200265 4500008004100000022001400041245010800055210006900163260000800232300001100240490000800251520162600259653001801885653001401903653002001917653001801937653002301955653002601978100002302004700002102027700001702048700002602065700002502091856013002116 2022 eng d a0022-328X00aReactivity of four coordinate iridium complex towards hydrogen: an experimental and computational study0 aReactivity of four coordinate iridium complex towards hydrogen a cMAY a1223170 v9653 a

Reaction of a four coordinate, 16-electron Ir complex, [Ir-(iPr)4(POCOP)(PPh3)] (4 ) (((iPr)4)(POCOP= 2,6-bis(di-isopropyl phosphinito)benzene, kappa(3)-C6H3-1,3-[OP((iPr))(2)](2)), with H-2 resulted in an oxidative addition product, cis-dihydride complex, cis-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( cis-5 ) presumably via the intermediacy of a sigma complex, [Ir(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)]. The cis-dihydride complex completely isomerizes to the trans-dihydride complex trans-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( trans-5 ) under ambient conditions in about 3 h. It was found that the steric and electronic features on the iridium center have significant influence on the approach of H-2 onto the metal center followed by oxidative addition and isomerization. The isomerization process was studied in detail and all the mechanistic aspects have been elucidated using a combination of both experimental work and computation. The cis-dihydride complex isomerizes to the trans-dihydride by compensating the trans influence of the strongly trans-directing hydride ligand. A mechanism involving the exchange of the position of PPh3 with a hydride ligand cis to itself via PPh3 dissociation and re-coordination thereby resulting in the formation of the trans-dihydride complex, has been proposed for the isomerization. The cis-dihydride was found to be a highly active catalyst for hydrogenation of ethy-lene. A competing reactivity study of cis-dihydride between isomerization versus insertion of C2H4 into the Ir-H bond, was studied experimentally and computationally. (c) 2022 Elsevier B.V. All rights reserved.

10aHydrogenation10aInsertion10airidium complex10aisomerization10aOxidative addition10aReductive elimination1 aAgrawal, Nisha, K.1 aDash, Soumya, R.1 aVanka, Kumar1 aNethaji, Munirathinam1 aJagirdar, Balaji, R. uhttps://library.ncl.res.in/content/reactivity-four-coordinate-iridium-complex-towards-hydrogen-experimental-and-computational02397nas a2200181 4500008004100000022001400041245013000055210006900185260000800254300001200262490000700274520172800281100002302009700002102032700001702053700002502070856012002095 2023 eng d a0276-733300aDual routes toward observation of a trans-H2/hydride complex in an iridium pincer system and hydrogenation catalytic activity0 aDual routes toward observation of a transH2hydride complex in an cMAR a441-4560 v423 a

The Abstraction of chloride from a six- coordinate complex, trans-[ Ir(H)(Cl)((iPr)4)(POCOP)(PPh3)] (1) [((iPr)4)(POCOP) = 2,6-bis(di-iso-propylphosphinito)benzene,kappa(3)-C6H3-1,3-[OP(Pr-i)(2 )](2)], using NaBAr4f leads to the generation of a dinitrogen complex, trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)][BAr4f] (6). Addition of H-2 to [Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)](+) (6) under extremely mild conditions (1 bar, 298 K) resulted in the reversible coordination of H-2 to generate the cis-[Ir(H)(eta H-2-(2))((iPr)4)(POCOP)(PPh3)](+) (cis-11) complex. The cis-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) complex (cis-11) isomerized to a trans isomer, trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) (trans-11), at 253 K. The isomerization process has been studied and supported by computations. Employing an alternative route, protonation of the trans-[Ir(H)(2)((iPr)4)(POCOP)(PPh3)] complex (2) at 183 K resulted in the formation of an identical, trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) complex (trans-11); upon warming the sample, the trans-H-2/hydride complex isomerized to the cis isomer above 253 K. Two independent routes to obtain trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) (trans-11) species have been established. Reaction of trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)][BAr4f] (6) with C2H4 gave the cis-[Ir(H)(eta(2)-C2H4)((iPr)4)(POCOP)(PPh3)](+) complex (cis-15), which also undergoes isomerization to yield an equilibrium mixture of cis/trans-[Ir(H)(eta(2)-C2H4)((iPr)4)(POCOP)(PPh3)](+) complexes (cis-15 and trans-15) at 253 K. The trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)](+) complex (6) is an excellent catalyst for hydrogenation of ethylene to ethane under very mild conditions.

1 aAgrawal, Nisha, K.1 aDash, Soumya, R.1 aVanka, Kumar1 aJagirdar, Balaji, R. uhttps://library.ncl.res.in/content/dual-routes-toward-observation-trans-h2hydride-complex-iridium-pincer-system-and01154nas a2200193 4500008004100000022001400041245011400055210006900169260000900238300001600247490000700263520045600270100002300726700002100749700002100770700001700791700002500808856012700833 2023 eng d a1477-922600aH-atom site exchange in an iridium trans-dihydrogen/hydride complex, trans-[Ir(H)(?2-H2)(iPr)4(POCOP)(DMAP)]+0 aHatom site exchange in an iridium transdihydrogenhydride complex cOCT  a13858-138630 v523 a

Treatment of trans-[Ir(H)(N)(2)((iPr)4)(POCOP)(DMAP)][BAr4f] (2) with H-2 (1 bar) under ambient conditions (298 K) results in the formation of a trans-[Ir(H)(?(2)-H-2)((iPr)4)(POCOP)(DMAP)][BAr4f] (3) complex. Complex 3 exhibits H-atom site exchange between the bound H-2 and the hydride ligands which are mutually trans to one another. A plausible mechanism of this exchange involves metal-ligand cooperativity as studied by computations.

1 aAgrawal, Nisha, K.1 aGayathridevi, S.1 aDash, Soumya, R.1 aVanka, Kumar1 aJagirdar, Balaji, R. uhttps://library.ncl.res.in/content/h-atom-site-exchange-iridium-trans-dihydrogenhydride-complex-trans-irh2-h2ipr4pocopdmap03387nas a2200193 4500008004100000245021900041210007100260260000800331300001400339490000700353520256500360100002202925700002302947700002202970700002102992700001703013700002403030856013903054 2024 eng d00aCrystal engineering for intramolecular π-π stacking: effect of substitution of electron-donating and electron-withdrawing groups on the molecular geometry in conformationally flexible Sulfoesters and sulfonamides0 aCrystal engineering for intramolecular ππ stacking effect of sub cJUL a3557-35730 v263 a

A series of 21 sulfoester and sulfonamide derivatives comprising two aromatic rings was synthesized to investigate the effect of the presence of either electron-donating (ED) or electron-withdrawing (EW) groups on the intramolecular pi-stacking assembly. The positioning of ED or EW moieties was carried out directly on one of the aromatic rings linked to the sulfonyl or sulfonamide moieties. In contrast, the other aromatic ring (phenyl or pyridine) was connected by a -CH2-CH2- spacer with the sulfonyl or sulfonamide moiety. The purpose of having an ethyl spacer between the two aromatic rings was to achieve conformational flexibility, facilitating the intramolecular pi-stacking assembly between the two aromatic rings. The use of sulfoester/sulfonamide groups allowed more conformational flexibility to attain desired orientations in solids with the interplay of the hydrogen-bonding interactions. Between the two functional groups, sulfonamides offered a more hydrogen-rich environment due to the amine moiety and may exhibit higher H-bonding propensity than the sulfoester moiety. The central idea here was to study the interplay between the hydrogen-bonding and pi & ctdot;pi interactions. The substituent groups chosen were categorized as strong electron-withdrawing (-CF3 and -CN), weak electron-withdrawing (-Cl and -Br), neutral (-H), and good electron-donating (-CH3 and -OCH3) groups. Crystal structure analysis revealed the syn conformation for all the derivatives, enabling intramolecular pi & ctdot;pi interactions between the two aromatic rings, whereas in the sulfonamide derivatives, the molecule takes either midway or anti conformations, except for one pyridine sulfonamide derivative, which showed the syn orientation but lacked intramolecular pi-stacking interactions. The absence of any conventional H-bond forming functional groups in the sulfoester derivatives may have resulted in the syn geometry facilitated by intramolecular pi-stacking interactions. Conversely, H-bond-forming functional groups in the sulfonamide derivatives could have prevented the syn conformation. The conformational analysis carried out employing density functional theory (DFT) calculations confirmed the higher stability of the syn conformation over the midway and anti orientations. The placing of electron-withdrawing and electron-donating groups at the para position of the benzene revealed sulfoesters preferably adopts a syn geometry facilitating the intramolecular pi-stacking, but sulphonamides takes midway or anti-geometry.

1 aShaikh, Samir, R.1 aGawade, Rupesh, L.1 aDabke, Niteen, B.1 aDash, Soumya, R.1 aVanka, Kumar1 aGonnade, Rajesh, G. uhttps://library.ncl.res.in/content/crystal-engineering-intramolecular-%CF%80-%CF%80-stacking-effect-substitution-electron-donating-and02488nas a2200277 4500008004100000022001400041245010000055210006900155260000800224520154900232653001701781653000801798653003001806653002701836653001701863100002401880700001901904700002101923700002101944700002801965700002201993700002502015700001702040700002402057856012902081 2024 eng d a1060-132500aDesigning of imine thiophene-ligated metal-complexes and implication in ethylene polymerization0 aDesigning of imine thiopheneligated metalcomplexes and implicati cSEP3 a

Polyethylene is the single largest volume polymer produced globally using Ziegler-type catalysts. Numerous modifications have been reported in search of a better catalyst that can control molecular weight, polydispersity, and branching. In our attempts to identify a suitable imine thiophene-ligated chromium complex, we examined 9 different titanium complexes computationally. The DFT investigations considered barriers for insertion, propagation, and termination by beta-H elimination or chain transfer, and identified N-(4-methoxyphenyl)-2-phenyl-1-(thiophen-2-yl)ethan-1-imine(L9) as the most suitable ligand. Subsequently, L9 was prepared in good yield (70%) by condensing 2-phenyl-1-(thiophen-2-yl)ethan-1-one with 4-methoxyaniline. Ligand L9 was treated with early transition metal precursors (Ti, Cr, Zr) to generate a homogenous catalyst. The identity of these catalysts was unambiguously ascertained using a combination of NMR, ICP, FT-IR, UV-Vis spectroscopy, and ESI-MS. The performance of L9-ligated titanium complex [Cat.1] was examined in ethylene polymerization using MMAO as a co-catalyst. Insertion of ethylene was tracked using high-pressure NMR experiments and Cat.1 was found to be active in the polymerization. Ethylene polymerization conditions were optimized to obtain high activity and molecular weight polyethylene. The chromium complex [Cat.2] outperformed the Ti and Zr-derived catalysts with the highest TOF of 6294 mol of PE/mol of Cr/h. Cat.2 produced high molecular weight, high-density polyethylene.

10aCr-complexes10aDFT10ahigh-density polyethylene10aImine thiophene ligand10aPolyethylene1 aShaikh, Maulali, H.1 aRamekar, Rohan1 aJawoor, Shailaja1 aDash, Soumya, R.1 aBirajadar, Rajkumar, S.1 aPawal, Sandip, B.1 aThenmani, Nandakumar1 aVanka, Kumar1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/designing-imine-thiophene-ligated-metal-complexes-and-implication-ethylene-polymerization01496nas a2200217 4500008004100000022001400041245012100055210006900176260000800245300001400253490000700267520072100274100002400995700002201019700002101041700001901062700001701081700002401098700002401122856013201146 2025 eng d a1528-748300aSynthesis and concomitant polymorphs of green fluorescence protein chromophore-anthracene-based fluorescent analogue0 aSynthesis and concomitant polymorphs of green fluorescence prote cFEB a1011-10220 v253 a

Controlled variations in fluorescence properties hold significant promise for applications in optical sensors, bioimaging, and advanced display devices. However, constructing multicolor fluorescent systems remains a challenge. In this study, we demonstrate the development of multicolor fluorescence by generating polymorphs of a novel green fluorescent protein chromophore analogue, which exhibits distinct photoluminescence emissions in the solid state. The observed emission variations are attributed to differences in molecular conformation due to variations in pi-stacking interactions between the polymorphs. This offers a novel approach to designing materials with tunable fluorescence properties.

1 aMali, Bhupendra, P.1 aDabke, Niteen, B.1 aDash, Soumya, R.1 aBiswas, Anupam1 aVanka, Kumar1 aManoj, Kochunnoonny1 aGonnade, Rajesh, G. uhttps://library.ncl.res.in/content/synthesis-and-concomitant-polymorphs-green-fluorescence-protein-chromophore-anthracene-based