02845nas a2200181 4500008004100000022001400041245013600055210006900191260007100260300001600331490000800347520210200355100001702457700001902474700001602493700002402509856013002533 2010 eng d a1932-744700aDFT Study of lewis base interactions with the MgCl2 surface in the ziegler-natta catalytic system: expanding the role of the donors0 aDFT Study of lewis base interactions with the MgCl2 surface in t a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a15771-157810 v1143 a

We present a computational study, using density functional theory, of the role of internal and external donors in supported heterogeneous Ziegler-Natta polymerization catalyst systems. The focus of the investigation is the ability of the donors to stabilize the MgCl2 support through the zip mode of coordination. Phthalates and alkoxy benzoates have been considered as representative internal and external donors, respectively. Models for the alpha (ccp) and the beta (hcp) phases of the (110) MgCl2 lateral cut have been considered. Studies were first done with a ``Fully Fixed Model'', where the atoms in the MgCl2 lateral cuts were kept fixed. The studies indicated that the phthalate donors would preferentially stabilize the alpha phase of MgCl2, while the alkoxy benzoate donors would stabilize the beta phase more, corroborating experimental results. A comparison of the zip coordination mode with other modes of coordination (mono, chelate, and bridge) indicates that it would be preferred over the mono and chelate coordination modes and be competitive with the bridge coordination mode. The validity of the Fully Fixed Model was then tested by doing calculations with the Partially Relaxed (some of the magnesium and chlorine atoms unfixed) and the Fully Relaxed (all atoms free) Models. The results from the latter two models corrected some of the discrepancies that had been observed for the Fully Fixed Model in comparison to previous experimental and computational investigations but were in general agreement with the Fully Fixed Model, indicating that the overall conclusions drawn with the earlier model are correct. Insertion studies done on an octahedrally coordinated titanium site flanked by two zip-coordinated phthalate donor molecules indicated that the zip-coordinating donors can confer exceptional regioselectivity to the titanium center. A list of potential donors that could serve as external donors, with di-iso-butyl phthalate (DIBP) as the internal donor, was investigated, and it was found that 1,3-diethers would serve as the best external donors to DIBP.

1 aVanka, Kumar1 aSingh, Gurmeet1 aIyer, Divya1 aGupta, Virendra, K. uhttps://library.ncl.res.in/content/dft-study-lewis-base-interactions-mgcl2-surface-ziegler-natta-catalytic-system-expanding-000918nas a2200157 4500008004100000022001400041245010700055210006900162260011000231300001600341490000700357520024000364100001600604700001700620856012300637 2011 eng d a1359-734500aDFT investigation of the potential of porous cages for the catalysis of ammonia borane dehydrogenation0 aDFT investigation of the potential of porous cages for the catal aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a11417-114190 v473 a

Full DFT based quantum mechanical studies reveal that zero dimensional porous structures, especially the newly proposed phosphorus incorporated organic cages, can be excellent catalysts for the dehydrogenation of ammonia borane.

1 aPal, Amrita1 aVanka, Kumar uhttps://library.ncl.res.in/content/dft-investigation-potential-porous-cages-catalysis-ammonia-borane-dehydrogenation-002013nas a2200169 4500008004100000022001400041245010400055210006900159260007100228300001400299490000700313520132800320100001901648700002701667700001701694856013201711 2014 eng d a0276-733300aDonor decomposition by lewis acids in Ziegler-Natta catalyst systems: a computational investigation0 aDonor decomposition by lewis acids in ZieglerNatta catalyst syst a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a4357-43670 v333 a

The development of new donors (Lewis bases, usually containing oxygen atoms) is one of the chief areas of research in Ziegler-Natta (ZN) olefin polymerization systems. The addition of such donors has led to improvement in the activity and selectivity of ZN systems. However, in order for the donor to be effective, it has to be chemically stable and resistant to decomposition by Lewis acidic species such as AlEt3. Discussed in the current work is the chemical stability of different ester donors, including aromatic benzoate donors and the silyl ester-a promising new donor class in ZN systems. Full quantum chemical calculations with density functional theory (DFT) indicate that esters can undergo decomposition through different pathways upon interaction with species such as the AlEt3 dimer: Al2Et6. Moreover, the studies show that the active, supported titanium catalyst species can cause donor decomposition and, in fact, is likely to be the greater threat to donor decomposition than Al2Et6. This explains why the addition of excess donors can lead to the poisoning of the active site in ZN systems. We have also computationally investigated means of improving the silyl ester donors in order to make them more robust and resilient to donor decomposition by Al2Et6 and the supported active titanium species.

1 aKumawat, Jugal1 aGupta, Virendra, Kumar1 aVanka, Kumar uhttps://library.ncl.res.in/content/donor-decomposition-lewis-acids-ziegler-natta-catalyst-systems-computational-investigation-000898nas a2200253 4500008004100000245011700041210006900158260000800227300001400235490000700249100001800256700002400274700002300298700002000321700002100341700002600362700002600388700002500414700001700439700001800456700001900474700002000493856013100513 2016 eng d00aDecoding the morphological diversity in two dimensional crystalline porous polymers by core planarity modulation0 aDecoding the morphological diversity in two dimensional crystall cJUN a7806-78100 v551 aHalder, Arjun1 aKandambeth, Sharath1 aBiswal, Bishnu, P.1 aKaur, Gagandeep1 aRoy, Neha, Chaki1 aAddicoat, Matthew, A.1 aSalunke, Jagadish, K.1 aBanerjee, Subhrashis1 aVanka, Kumar1 aHeine, Thomas1 aVerma, Sandeep1 aBanerjee, Rahul uhttps://library.ncl.res.in/content/decoding-morphological-diversity-two-dimensional-crystalline-porous-polymers-core-planarity01169nas a2200169 4500008004100000245007500041210006900116260000800185300001400193490000700207520060300214100002400817700001900841700001500860700001700875856010700892 2017 eng d00aDBU-mediated diastereoselective aldol-type cyanomethylation of isatins0 aDBUmediated diastereoselective aldoltype cyanomethylation of isa cAPR a4489-44960 v823 aAn efficient, metal-free approach to 3-substituted 3-hydroxybxindole by DBU-mediated highly diastereoselective addition of aryl acetonitrile to N-protected isatin under mild conditions has been developed. The reaction proceeds smoothly to produce respective cyanomethylated adducts in good yield and excellent diastereoselectivity. Further transformation of the cyanide group allowed the synthesis of an advance intermediate of corresponding (+/-) CPC analogue. The mechanistic insight :toward the aldol-type cyanomethylation, of N-tritylisatin with benzyl cyanide was obtained by DFT calculations.1 aRao, V., U. Bhaskar1 aKumar, Krishna1 aDas, Tamal1 aVanka, Kumar uhttps://library.ncl.res.in/content/dbu-mediated-diastereoselective-aldol-type-cyanomethylation-isatins01113nas a2200193 4500008004100000022001400041245012400055210006900179260000800248300001400256490000700270520042200277100001700699700002000716700001800736700001700754700002000771856012800791 2019 eng d a1477-052000aDiastereoselective multi-component tandem condensation: synthesis of 2-amino-4-(2-furanone)-4H-chromene-3-carbonitriles0 aDiastereoselective multicomponent tandem condensation synthesis  cOCT a8853-88570 v173 a

A general strategy for a one-pot stereoselective synthesis of 2-amino-4-(2-furanone)-4H-chromene-3-carbonitriles by reaction of salicylaldehyde, malononitrile and butenolides via a tandem Knoevenagel/Pinner/vinylogous Michael condensation is presented. The beta,gamma-butenolides gave a syn-selective MCR adduct with a dr up to 11.5 : 1. The mechanistic insight into the MCR was obtained by DFT calculations.

1 aGupta, Vijay1 aSahu, Debashish1 aJain, Shailja1 aVanka, Kumar1 aSingh, Ravi, P. uhttps://library.ncl.res.in/content/diastereoselective-multi-component-tandem-condensation-synthesis-2-amino-4-2-furanone-4h00974nas a2200193 4500008004100000022001400041245010700055210006900162260000900231300001600240490000700256520029500263100001700558700002400575700001800599700001700617700001900634856012700653 2021 eng d a1359-734500aDeoxygenative hydroboration of primary and secondary amides: a catalyst-free and solvent-free approach0 aDeoxygenative hydroboration of primary and secondary amides a ca cOCT  a10596-105990 v573 aIn contrast to the recent reports on catalytic hydroboration of amides to amines with pinacolborane (HBpin), a simple catalyst-free and solvent-free method for the hydroboration of a variety of amides has been realized. To get the mechanistic insights, DFT calculations have been performed.1 aKumar, Rohit1 aBisai, Milan, Kumar1 aJain, Shailja1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/deoxygenative-hydroboration-primary-and-secondary-amides-catalyst-free-and-solvent-free01122nas a2200217 4500008004100000022001400041245007300055210006900128260000900197300001400206490000700220520043800227100001700665700002300682700002400705700001900729700001500748700001700763700001900780856010500799 2021 eng d a1359-734500aDiverse reactivity of carbenes and silylenes towards fluoropyridines0 aDiverse reactivity of carbenes and silylenes towards fluoropyrid cMAY  a4428-44310 v573 a

The reaction of IDipp with C5F5N led to functionalization of all three carbon atoms of the imidazole ring with HF2- as the counter-anion (1). Reactivity with 2,3,5,6-tetrafluoropyridine gives only C-F bond activation leaving C-H bonds intact (5b). The reaction of SIDipp with C5F5N in the presence of BF3 afforded the ring cleavage product (3). Analogous reactions with silylene led to oxidative addition at the Si(II) center.

1 aKundu, Gargi1 aAjithkumar, V., S.1 aBisai, Milan, Kumar1 aTothadi, Srinu1 aDas, Tamal1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/diverse-reactivity-carbenes-and-silylenes-towards-fluoropyridines01891nas a2200193 4500008004100000022001400041245011100055210006900166260000900235300001400244490000700258520120400265100002401469700002601493700001501519700001701534700001901551856012701570 2021 eng d a0020-166900aDiverse reactivity of hypersilylsilylene with boranes and threecomponent reactions with aldehyde and HBpin0 aDiverse reactivity of hypersilylsilylene with boranes and threec cFEB  a1654-16630 v603 a

The recently reported hypersilylsilylene PhC-(NtBu)(2)SiSi(SiMe3)(3) (1) reacts with BH3, 9-BBN, and PhBCl2 to yield the respective Lewis acid base adducts 2-4, respectively. Compound 4 undergoes isomerization to form a ring expansion product 5. The same silylene was found to initially form an adduct with HBpin (6) and subsequently isomerized to 7 via the rupture of the B-H bond of HBpin (7), where the hydride was bound to the carbon atom of the amidinate ligand and the Bpin unit was attached to the silicon center. Surprisingly, the reaction of 1 with HBcat results in PhC(NtBu)(2)Bcat (8). Subsequently, we have shown that HBcat forms the same product when it reacts with related silylene PhC(NtBu)(2)SiN(SiMe3)(3) (1'). With all of these reactions in hand, we ponder if silylene can activate two small molecules at one time. In this work, we delineate the three-component reactions of silylenes 1 and 1' with 4-fluorobenzaldehyde and HBpin, which afforded unusual coupling products, 9 and 10, respectively. Note that 9 and 10 were prepared from the cleavage of the B-H and C=O bonds by silylene in a single reaction and are the first structurally attested Si-C-O-B coupled products.

1 aBisai, Milan, Kumar1 aSwamy, V., S. V. S. N1 aRaj, Vipin1 aVanka, Kumar1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/diverse-reactivity-hypersilylsilylene-boranes-and-threecomponent-reactions-aldehyde-and03504nas a2200253 4500008004100000022001400041245018200055210006900237260000800306300001600314490000700330520257000337100002302907700002502930700002902955700001602984700001803000700002503018700001703043700002303060700001903083700001703102856013103119 2022 eng d a2050-752600aDirect (hetero)arylation (DHAP) polymerization of conjugated polymers - new A-B-A monomer design for P(NDI2OD-T2) & the challenges of adopting DHAP for continuous flow processes0 aDirect heteroarylation DHAP polymerization of conjugated polymer cSEP a13025-130390 v103 a

P(NDI2OD-T2), also known as Polyera ActivInk N2200, was synthesized by the atom-economic direct hetero arylation polymerization (DHAP) route using a newly designed A-B-A monomer. The new monomer design involved flanking naphthalene diimide with bithiophene units in the bay position, which was further polymerized with bay substituted 1,4-dibromo naphthalene diimide, to afford the same polymer structure as P(NDI2OD-T2). The new monomer design resulted in a very high molecular weight (M-n: 99.5 kDa, D-M: 2.8) defect-free polymer in a quantitative yield by the DHAP batch process using 1,2,4-trichlorobenzene (TCB) as the solvent. DFT studies revealed that the abstraction of the alpha-proton from the naphthalene diimide substituted 2,2 `-bithiophene was favorable by 2.6 kcal mol(-1) (Delta Delta G) as compared to that from 2,2 `-bithiophene. The reason for this improved C-H activation at the alpha position can be attributed to the presence of C-HMIDLINE HORIZONTAL ELLIPSIS pi stabilizing interactions in naphthalene diimide substituted 2,2 `-bithiophene, which strengthens upon the extended charge delocalization throughout the ring, thus stabilizing the conjugate base generated after the proton abstraction. Continuous flow polymerization was carried out by pumping the DHAP reaction mixture including the monomers, catalyst, and additive (pivalic acid) solubilized in degassed TCB through a pre-heated glass condenser packed with K2CO3 and Celite under aerobic conditions. Reproducible molecular weights of M-n: 29.5 kDa, D-M: 1.7 were obtained at much lower concentrations of reactant mixture compared to that for batch polymerization. This is the first report of the synthesis of P(NDI2OD-T2) by a Continuous Flow Process adopting the DHAP route to obtain a defect-free polymer with reasonable molecular weights. P(NDI2OD-T2) was also synthesized by Stille polymerization as a reference control sample to compare the thermal and charge carrier transport properties of the DHAP polymers. Organic field-effect (OFET) mobility measurements indicated mobility values in the order of 10(-3) cm(2) V-1 s(-1) for the DHAP batch polymer (using the novel monomer design). The P(NDI2OD-T2) synthesized by DHAP batch using the commonly used starting materials - bisbromo naphthalene diimide and bithiophene, exhibited OFET mobilities which were one order less, similar to 10(-4) cm(2) V-1 s(-1). This observation highlights the importance of structural design in the monomer to enhance reactivity and thereby the bulk properties using the DHAP route.

1 aKakde, Navnath, R.1 aBharathkumar, H., J.1 aWavhal, Bhaiyyasaheb, A.1 aNikam, Arun1 aPatil, Suneha1 aDash, Soumya, Ranjan1 aVanka, Kumar1 aKrishnamoorthy, K.1 aKulkarni, Amol1 aAsha, S., K. uhttps://library.ncl.res.in/content/direct-heteroarylation-dhap-polymerization-conjugated-polymers-new-b-monomer-design-pndi2od01145nas a2200205 4500008004100000022001400041245013700055210006900192260000800261300001400269490000700283520039700290100002100687700002100708700002500729700001900754700001700773700002200790856012700812 2022 eng d a1477-052000aDirect oxidation of bromo-derived Fischer-Borsche oxo-ring using molecular iodine with combined experimental and computational study0 aDirect oxidation of bromoderived FischerBorsche oxoring using mo cJUL a5726-57290 v203 a

A direct oxidation of the bromo-derived Fischer-Borsche oxo-ring leading to carbazolequinone has been developed by using molecular iodine. This unprecedented transformation has been used for the modular synthesis of the anti-cardiotonic agent murrayaquinone. Furthermore, the present method has been generalized to a broad range of functional groups, with good to excellent yield.

1 aHumne, Vivek, T.1 aGhom, Monica, H.1 aNaykode, Mahavir, S.1 aDangat, Yuvraj1 aVanka, Kumar1 aLokhande, Pradeep uhttps://library.ncl.res.in/content/direct-oxidation-bromo-derived-fischer-borsche-oxo-ring-using-molecular-iodine-combined02397nas 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-and02102nas a2200289 4500008004100000022001400041245013100055210006900186260000800255300001400263490000700277520110200284653001301386653003201399653002901431653002101460653002101481653001901502100002601521700002301547700002501570700002301595700002501618700001701643700002501660856012701685 2024 eng d a2155-543500aDehydrogenative coupling of alcohols with internal alkynes under nickel catalysis: an access to β-deuterated branched ketones0 aDehydrogenative coupling of alcohols with internal alkynes under cMAY a8294-83090 v143 a

In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C-C and C-N bond-forming reactions via the dehydrogenative borrowing hydrogen strategy in traditional transition metal catalysis; however, as an acylating agent in the C-C bond-forming reactions is challenging and rarely reported. Here, we report the dehydrogenative coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol is used as an acylating agent. This reaction system affords a wide range of alpha-branched aryl ketone derivatives with zero waste generation through the umpolung borrowing hydrogen strategy. Moreover, we have demonstrated the chemodivergent applications of the alpha-disubstituted ketones to other valuable building blocks, including large-scale synthesis of beta-deuterated branched ketones. Several spectroscopic studies, intermediate identification, and density functional theory calculations were performed to elucidate the reaction mechanism.

10aAlcohols10aalpha-branched aryl ketones10adehydrogenative coupling10ainternal alkynes10anickel catalysis10apseudoumpolung1 aSubaramanian, Murugan1 aGouda, Chandrakant1 aRoy, Triptesh, Kumar1 aGanesan, Sivakumar1 aBanerjee, Subhrashis1 aVanka, Kumar1 aBalaraman, Ekambaram uhttps://library.ncl.res.in/content/dehydrogenative-coupling-alcohols-internal-alkynes-under-nickel-catalysis-access-%CE%B202488nas 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-polymerization02337nas a2200253 4500008004100000022001400041245006900055210006800124260000800192490000700200520155700207653001501764653001501779653002101794653001601815653001801831100002101849700003301870700001901903700002601922700001701948700002001965856009801985 2025 eng d a1864-563100aDepolymerization of waste polycarbonates to value-added products0 aDepolymerization of waste polycarbonates to valueadded products cJAN0 v183 a

Additive free aminolysis method developed for the depolymerization/upcycling of polycarbonates. We report here chemical recycling of polycarbonate under ambient conditions to get its monomer bisphenol A, monoaminocarbamate and biscarbamates in 1 : 2 : 1 ratio respectively. By employing the secondary amine as the aminating reagent, facilitates the depolymerization to work under additive/catalyst free conditions. The developed method deals with depolymerization of waste polycarbonates and works even with late-stage amine derivatives such as amoxapine and desloratadine which are drugs molecules known to treat neurotic disorders and allergies respectively. The reaction can be scaled up and works with similar efficacy which depicts the efficiency of the depolymerization of wasteend-of-life polycarbonate plastic waste. The biscarbamate and bisphenol-A was further subjected for the post functionalization to obtain amides and phenol in good yields. Developed additive/catalyst free aminolysis of waste polycarbonates to carbamates and monomer BPA at ambient conditions. Variety of secondary amines were screened including the late stage amine derivatives like amoxapine and desloratadine which delivered the expected products successfully. Later the developed methodology was even applied for the different end-of-life polycarbonates with the secondary amine and achieved the depolymerization without any obstacle. Further carried out the scale up reaction and derivatization of carbamates and BPA to amide and phenol synthesis. image

10aAminolysis10acarbamates10adepolymerization10aEnd-of-life10aPolycarbonate1 aPadhi, Ganeshdev1 aPansare, Vaibhav, Ramachandr1 aBajpai, Priyam1 aKrishna, Gamidi, Rama1 aVanka, Kumar1 aBarsu, Nagaraju uhttps://library.ncl.res.in/content/depolymerization-waste-polycarbonates-value-added-products02640nas a2200289 4500008004100000022001400041245015900055210006900214260000800283300001100291490000800302520162200310653002401932653002101956653002401977653003102001653002502032653001902057653001802076100002602094700001602120700001702136700001702153700003002170700002702200856012302227 2025 eng d a1010-603000aDouble anchoring squaraine dye with triazatruxene amine donor for dye-sensitized solar cells: sequential cosensitization for panchromatic light-harvesting0 aDouble anchoring squaraine dye with triazatruxene amine donor fo cMAY a1162290 v4623 a

Dyes are firmly bound to a semiconducting TiO2 film using carboxylic acid anchoring groups for an efficient electron transfer from the excited state of dye to the conduction band (CB) of TiO2. Strong dye binding can be accomplished with multi-anchoring dye designs to improve photophysical characteristics, including high extinction coefficients, panchromatic absorption, post-sensitization modifications, and dark current suppression, besides enhancing the stability of the dye-TiO2 interface. Herein, a novel KV2D dye with double squaraine acceptor and double carboxylic acid anchoring groups is designed to achieve a high extinction coefficient (epsilon, 3.57 x 105M-1cm-1) and robust binding to the TiO2 film for an effective electron transfer. We systematically changed the amount of coadsorbent chenodeoxycholic acid (CDCA) to control the aggregation of dyes on the TiO2 surface that improves the power conversion efficiency (PCE, eta) for the devices based on the doubleanchoring KV2D. Out of these devices, KV2D: CDCA (1:10) based cell exhibited the best PCE of 5.26% with VOC of 754 mV, JSC of 10.41 mA/cm2, and ff of 67%. The sequential cosensitization studies were carried out with a far-red active dye to find the effect of the strong binding of the sensitizer to the TiO2 film. Interestingly, when di-anchoring, KV2D was sensitized first for 12 h and then sequentially cosensitized with far-red absorbing SQS4 for 5 h to achieve a PCE of 5.0% with VOC of 697 mV, JSC of 10.23 mA/cm2, and ff of 70% with panchromatic spectral response in IPCE upto 730 nm giving higher photocurrent generation.

10aaggregation of dyes10aBulky donor unit10aDouble acceptor dye10aDye-sensitized solar cells10aself-assembly of dye10asquaraine dyes10atriazatruxene1 aIngole, Kiran, Balaso1 aSiby, Jesna1 aPandya, Rinu1 aVanka, Kumar1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/double-anchoring-squaraine-dye-triazatruxene-amine-donor-dye-sensitized-solar-cells