01677nas a2200193 4500008004100000022001400041245009400055210006900149260000800218300001600226490000700242520098400249100001801233700002801251700003001279700002301309700003001332856012101362 2015 eng d a1359-734500aSeeded on-surface supramolecular growth for large area conductive donor-acceptor assembly0 aSeeded onsurface supramolecular growth for large area conductive cMAY a10439-104420 v513 a

Charge transport features of organic semiconductor assemblies are of paramount importance. However, large-area extended supramolecular structures of donor-acceptor combinations with controlled self-assembly pathways are hardly accessible. In this context, as a representative example, seeded on-surface supramolecular growth of tetrathiafulvalene and tetracyano-p-quinodimethane (TTF-TCNQ) using active termini of solution-formed sheaves has been introduced to form an extended assembly. We demonstrate for the first time, the creation of a large-area donor-acceptor assembly on the surface, which is practically very tedious, using a seeded, evaporation-assisted growth process. The excellent molecular ordering in this assembly is substantiated by its good electrical conductivity (similar to 10(-2) S cm(-1)). The on-surface assembly via both internally formed and externally added sheaf-like seeds open new pathways in supramolecular chemistry and device applications.

1 aGoudappagouda1 aChithiravel, Sundaresan1 aKrishnamoorthy, Kothandam1 aGosavi, Suresh, W.1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/seeded-surface-supramolecular-growth-large-area-conductive-donor-acceptor-assembly01786nas a2200205 4500008004100000022001400041245012000055210006900175260000900244300001600253490000800269520105100277100001901328700002701347700001701374700001601391700003001407700001701437856012601454 2016 eng d a0002-786300aCounteranion driven homochiral assembly of a cationic C-3-symmetric gelator through ion-pair assisted hydrogen bond0 aCounteranion driven homochiral assembly of a cationic C3symmetri cSEP  a11113-111160 v1383 a

The helical handedness in achiral self-assemblies is mostly complex due to spontaneous symmetry breaking or kinetically controlled random assembly formation. Here an attempt has been made to address this issue through chiral anion exchange. A new class of cationic achiral C-3-symmetric gelator devoid of any conventional gelation assisting functional units is found to form both right-and left-handed helical structures. A chiral counteranion exchange-assisted approach is successfully introduced to control the chirality sign and thereby to obtain preferred homochiral assemblies. Formation of anion-assisted chiral assembly was confirmed by circular dichroism (CD) spectroscopy, microscopic images, and crystal structure. The X-ray crystal structure reveals the construction of helical assemblies with opposite handedness for (+)- and (-)-chiral anion reformed gelators. The appropriate counteranion driven ion-pair-assisted hydrogen-bonding interactions are found responsible for the helical bias control in this C-3-symmetric gelator.

1 aMaity, Arunava1 aGangopadhyay, Monalisa1 aBasu, Arghya1 aAute, Sunil1 aBabu, Sukumaran, Santhosh1 aDas, Amitava uhttp://library.ncl.res.in/content/counteranion-driven-homochiral-assembly-cationic-c-3-symmetric-gelator-through-ion-pair01704nas a2200181 4500008004100000245012300041210006900164260000800233300001400241490000700255520098100262100001801243700003301261700003801294700003101332700003001363856012901393 2017 eng d00aCascade energy transfer and tunable emission from nanosheet hybrids: locating acceptor molecules through chiral doping0 aCascade energy transfer and tunable emission from nanosheet hybr cJUL a7072-70750 v533 aLight harvesting donor-acceptor assemblies are indispensable to efficiently tap photons. In an attempt to improve the light harvesting efficiency of an acceptor doped assembly, we design and synthesize a donor-acceptor-donor triad which exhibits an exceptional intramolecular energy transfer with excellent efficiency. Moreover, a facile cascade energy transfer (energy funnelling) is observed in the presence of a series of second acceptors (63-91% efficiency) with tunable emission colours. Self-assembled nanosheets formed by the triad in the presence of acceptors exhibit cascade energy transfer assisted tunable emission. In addition, use of chiral acceptors induces chirality to the triad and results in the formation of chiral nanosheets alongwith cascade energy transfer. Here chiral induction, nanosheet formation and cascade energy transfer in the presence of chiral acceptors are used as tools to probe the intercalation of acceptor molecules in the donor scaffold.1 aGoudappagouda1 aWakchaure, Vivek, Chandrakan1 aRanjeesh, Kayaramkodath, Chandran1 aAbhai, Chalona, Antony Ral1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/cascade-energy-transfer-and-tunable-emission-nanosheet-hybrids-locating-acceptor-molecules02529nas a2200409 4500008004100000022001400041245011800055210006900173260000800242490000700250520127700257653001301534653003001547653001401577653001501591653000801606653001001614653001801624653001601642653001901658653001901677653002101696653001001717653002301727653001401750100003001764700001901794700001801813700001901831700001901850700002401869700001701893700002701910700003001937700002801967856012401995 2017 eng d a0947-653900aMixed-stack charge transfer crystals of pillar[5]quinone and tetrathiafulvalene exhibiting ferroelectric features0 aMixedstack charge transfer crystals of pillar5quinone and tetrat cSEP0 v233 a

Ferroelectric materials find extensive applications in the fabrication of compact memory devices and ultra-sensitive multifunctional detectors. Face-to-face alternate stacking of electron donors and acceptors effectuate long-range unidirectional ordering of charge-transfer (CT) dipoles, promising tunable ferroelectricity. Herein we report a new TTF-quinone system-an emerald green CT complex consisting pillar[5]quinone (P5Q) and tetrathiafulvalene (TTF). The CT crystals, as determined by single crystal synchrotron X-ray diffraction, adopt a 1:1 mixed-stack arrangement of donor and acceptor with alternating dimers of TTF and 1,4-dioxane encapsulated P5Q. The TTF-P5Q.dioxane crystal possesses a macroscopic polarization axis giving rise to ferroelectricity at room temperature. The CT complex manifests ferroelectric features such as optical polarization rotation, temperature-dependent phase transition and piezoelectric response in single crystals. Ferroelectric behavior observed in P5Q-based CT complex widens the scope for further work on this structurally intriguing and readily accessible cyclic pentaquinone.

10aAcceptor10aCharge-transfer complexes10aChemistry10aConductors10aDDQ10aDonor10aferroelectric10aMacrocycles10aOrganic Metals10aPi-interaction10aPillar[5]quinone10asalts10aTransfer Complexes10aTransport1 aShivakumar, Kilingaru, I.1 aSwathi, Kadaba1 aGoudappagouda1 aDas, Tamal, C.1 aKumar, Ashwani1 aMakde, Ravindra, D.1 aVanka, Kumar1 aNarayan, Kavassery, S.1 aBabu, Sukumaran, Santhosh1 aSanjayan, Gangadhar, J. uhttp://library.ncl.res.in/content/mixed-stack-charge-transfer-crystals-pillar5quinone-and-tetrathiafulvalene-exhibiting01214nas a2200193 4500008004100000022001400041245011200055210006900167260000800236300001200244490000700256520050900263100002100772700002100793700002400814700003000838700002800868856012400896 2018 eng d a1359-734500aConducting nanofibres of solvatofluorochromic cyclohexanetrione-dithiolylidene-based C-3 symmetric molecule0 aConducting nanofibres of solvatofluorochromic cyclohexanetrioned cJAN a212-2150 v543 a

We report a novel set of easily tailorable C-3 symmetric molecules with a pi-extended core and adorned with different thioalkyl groups, exhibiting solvatofluorochromic and amphoteric redox behaviour. The nearly planar core exhibits intermolecular face-to-face pi-stacking, S...S and intramolecular S...O interactions. Current-sensing atomic force microscopy studies revealed a high conductivity of similar to 0.15 mS cm(-1) in the undoped J-aggregate nanofibres of the thiopropyl appended gelator.

1 aShivakumar, K.I.1 a., Goudappagouda1 aGonnade, Rajesh, G.1 aBabu, Sukumaran, Santhosh1 aSanjayan, Gangadhar, J. uhttp://library.ncl.res.in/content/conducting-nanofibres-solvatofluorochromic-cyclohexanetrione-dithiolylidene-based-c-301604nas a2200205 4500008004100000022001400041245008900055210006900144260000800213520090400221653001001125653001801135653002401153653001101177653001201188100003301200700001501233700003001248856012001278 2019 eng d a2192-650600aBoron-conjugated pyrenes as fluorescence-based molecular probes and security markers0 aBoronconjugated pyrenes as fluorescencebased molecular probes an cJUL3 a

Boron-embedded aromatic hydrocarbons are a class of molecules known for their distinct electronic and/or optoelectronic properties and are thus suitable for many potential applications. Among those, boronic ester and acid containing molecules have been widely used for sensing and molecular recognition applications, respectively. We compared the sensing and molecular recognition properties of two boron-containing pyrene derivatives for fluoride and glucose sensing applications. The presence of four boronate ester groups enabled fluoride ion sensing at the mu M level. The boronic acid derivative is very selective towards glucose compared to other saccharides. Furthermore, we used the mechano-responsive fluorescence changes and self-assembly of these derivatives, respectively, for fluorescence-based inkless and ink (water)-based writing in invisible security labeling applications.

10aboron10acarbohydrates10amechanoluminescence10apyrene10asensors1 aWakchaure, Vivek, Chandrakan1 aDas, Tamal1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/boron-conjugated-pyrenes-fluorescence-based-molecular-probes-and-security-markers00986nas a2200193 4500008004100000022001400041245014700055210006900202260000900271300001400280490000700294520021000301100001800511700003300529700003800562700003100600700003000631856013100661 2019 eng d a1359-734500aCascade energy transfer and tunable emission from nanosheet hybrids: locating acceptor molecules through chiral doping (vol 53, pg 7072, 2017)0 aCascade energy transfer and tunable emission from nanosheet hybr cJUN  a6462-64620 v553 a

Correction for `Cascade energy transfer and tunable emission from nanosheet hybrids: locating acceptor molecules through chiral doping' by Goudappagouda et al., Chem. Commun., 2017, 53, 7072-7075.

1 aGoudappagouda1 aWakchaure, Vivek, Chandrakan1 aRanjeesh, Kayaramkodath, Chandran1 aAbhai, Chalona, Antony Ral1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/cascade-energy-transfer-and-tunable-emission-nanosheet-hybrids-locating-acceptor-molecules-002444nas a2200217 4500008004100000245009700041210006900138260000800207300001400215490000700229520166200236100003301898700000501931700001801936700003801954700002301992700002602015700003402041700003002075856012102105 2019 eng d00aCharge transfer liquid: a stable donor-acceptor interaction in the solvent-free liquid state0 aCharge transfer liquid a stable donoracceptor interaction in the cAUG a9371-93740 v553 a

Charge-transfer complexes have been an inspiration to develop many functional soft materials. However, most of those studies have focused on solution based assemblies wherein the explicit control of solvents and their polarity are crucial. In this context, we explore an efficient and stable charge transfer liquid using a solvent-free liquid dialkoxynaphthalene donor and a naphthalenediimide acceptor. It has been observed that irrespective of the donor-acceptor ratio, the charge-transfer liquid exhibited an unprecedented stability and retained characteristic features even at increased temperatures. The underlying intermolecular interactions leading to efficient CT have been examined by NMR techniques together with theoretical modelling studies. The concept of charge transfer liquid will be highly beneficial for the development of processable optoelectronically active materials.
 

1 aWakchaure, Vivek, Chandrakan1 a1 aGoudappagouda1 aRanjeesh, Kayaramkodath, Chandran1 aChakrabarty, Suman1 aRavindranathan, Sapna1 aRajamohanan, Pattuparambil, R1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/charge-transfer-liquid-stable-donor-acceptor-interaction-solvent-free-liquid-state00941nas a2200193 4500008004100000022001400041245013500055210006900190260000900259300000900268490000700277520020700284100003000491700001800521700002400539700003000563700002800593856012600621 2019 eng d a1359-734500aConducting nanofibres of solvatofluorochromic cyclohexanetrione-dithiolylidene-based C-3 symmetric molecule (vol 54, pg 212, 2018)0 aConducting nanofibres of solvatofluorochromic cyclohexanetrioned cJUN  a64610 v553 a

Correction for `Conducting nanofibres of solvatofluorochromic cyclohexanetrione-dithiolylidene-based C-3 symmetric molecule' by Kilingaru I. Shivakumar et al., Chem. Commun., 2018, 54, 212-215.

1 aShivakumar, Kilingaru, I.1 aGoudappagouda1 aGonnade, Rajesh, G.1 aBabu, Sukumaran, Santhosh1 aSanjayan, Gangadhar, J. uhttp://library.ncl.res.in/content/conducting-nanofibres-solvatofluorochromic-cyclohexanetrione-dithiolylidene-based-c-3-002055nas a2200241 4500008004100000022001400041245009200055210006900147260000800216300001600224490000800240520121300248100003801461700002601499700002901525700001801554700003301572700001801605700001501623700002401638700003001662856012101692 2019 eng d a0002-786300aImidazole-linked crystalline two-dimensional polymer with ultrahigh proton-conductivity0 aImidazolelinked crystalline twodimensional polymer with ultrahig cSEP a14950-149540 v1413 a

Proton-exchange membrane fuel cells are promising energy devices for a sustainable future due to green features, high power density, and mild operating conditions. A facile proton-conducting membrane plays a pivotal role to boost the efficiency of fuel cells, and hence focused research in this area is highly desirable. Major issues associated with the successful example of Nafion resulted in the search for alternate proton conducting materials. Even though proton carrier loaded crystalline porous organic frameworks have been used for protonconduction, the weak host-guest interactions limited their practical use. Herein, we developed a crystalline 2D-polymer composed of benzimidazole units as the integral part, prepared by the condensation of aryl acid and diamine in polyphosphoric acid medium. The imidazole linked-2D-polymer exhibits ultrahigh proton conductivity (3.2 X 10(-2) S cm(-1)) (at 95% relative humidity and 95 degrees C) in the pristine state, which is highest among the undoped porous organic frameworks so far reported. The present strategy of a crystalline proton-conducting 2D-polymer will lead to the development of new high performing crystalline solid proton conductor.

1 aRanjeesh, Kayaramkodath, Chandran1 aIlathvalappil, Rajith1 aVeer, Sairam, Dnyaneshwa1 aPeter, Joseph1 aWakchaure, Vivek, Chandrakan1 aGoudappagouda1 aRaj, Vipin1 aKurungot, Sreekumar1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/imidazole-linked-crystalline-two-dimensional-polymer-ultrahigh-proton-conductivity01731nas a2200181 4500008004100000022001400041245009600055210006900151260000900220300001600229490000600245520108200251100002501333700002401358700001501382700003001397856012201427 2020 eng d a2050-748800aDual mode selective detection and differentiation of TNT from other nitroaromatic compounds0 aDual mode selective detection and differentiation of TNT from ot cJUN  a10767-107710 v83 a

Selective detection of explosives, especially TNT, is a highly desirable area of research and various explosives detection devices including fluorescent sensors are already in place. However, multi-mode sensors will be more useful and reliable than conventional fluorescent ``Turn Off'' sensors. One of the challenges is the development of selective sensors to prevent illegal transport of commonly used explosive TNT through on-the-spot analysis. In this context, we report a fluorescent polymer-based selective detection of TNT using both fluorometric and colorimetric signals. In addition, colorimetric differentiation of TNT from other nitroaromatic compounds is made possible by complexing with various amines. Even though many other sensors are available for TNT, the current demonstration is unique in terms of selectivity, sensitivity, reliability, portability, and rapidity of results. The as-developed explosive detection kit can be useful in both civilian and military operations to trace the illegal transport of TNT as well as for post-explosion analysis.

1 aPatil, Goudappagouda1 aDongre, Sangram, D.1 aDas, Tamal1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/dual-mode-selective-detection-and-differentiation-tnt-other-nitroaromatic-compounds02110nas a2200301 4500008004100000022001400041245007700055210006900132260000800201300001600209490000700225520116400232653001401396653001301410653002001423653003001443653001601473100002601489700001801515700002901533700003101562700001801593700002401611700002401635700002301659700003001682856009601712 2020 eng d a1433-785100aSelf-assembled helical arrays for the stabilization of the triplet state0 aSelfassembled helical arrays for the stabilization of the triple cJUL a13079-130850 v593 a

Room-temperature phosphorescence of metal and heavy atom-free organic molecules has emerged as an area of great potential in recent years. A rational design played a critical role in controlling the molecular ordering to impart efficient intersystem crossing and stabilize the triplet state to achieve room-temperature ultralong phosphorescence. However, in most cases, the strategies to strengthen phosphorescence efficiency have resulted in a reduced lifetime, and the available nearly degenerate singlet-triplet energy levels impart a natural competition between delayed fluorescence and phosphorescence, with the former one having the advantage. Herein, an organic helical assembly supports the exhibition of an ultralong phosphorescence lifetime. In contrary to other molecules, 3,6-phenylmethanone functionalized 9-hexylcarbazole exhibits a remarkable improvement in phosphorescence lifetime (>4.1 s) and quantum yield (11 %) owing to an efficient molecular packing in the crystal state. A right-handed helical molecular array act as a trap and exhibits triplet exciton migration to support the exceptionally longer phosphorescence lifetime.

10acarbazole10ahelicity10aphenylmethanone10aultralong phosphorescence10awaveguiding1 aNidhankar, Aakash, D.1 aGoudappagouda1 aKumari, Divya, S. Mohana1 aChaubey, Shailendra, Kumar1 aNayak, Rashmi1 aGonnade, Rajesh, G.1 aKumar, G., V. Pavan1 aKrishnan, Retheesh1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/self-assembled-helical-arrays-stabilization-triplet-state01895nas a2200241 4500008004100000022001400041245011600055210006900171260000800240300001100248490000800259520107900267653001301346653001701359653002001376653001901396100001801415700001801433700001801451700002301469700003001492856013101522 2020 eng d a0143-720800aTuning phosphorescence features of triphenylamines by varying functional groups and intermolecular interactions0 aTuning phosphorescence features of triphenylamines by varying fu cFEB a1079310 v1733 a

Organic room temperature phosphorescent materials are known for their synthetic feasibility, tunable phosphorescence wavelength and lifetime, etc. Hence new design strategies have been applied on various fluorophores to improve phosphorescence features. Among those, triphenylamines are phosphorescence active due to the presence of nitrogen atom, propeller molecular structure, and intermolecular interactions in the crystal state. Here we have studied the room temperature phosphorescence of a series of triphenylamines with various functional groups. Detailed studies have shown that the phosphorescence can be fine-tuned by functional group modification. A long phosphorescence lifetime around 100 ms at room temperature in air can be achieved by the interplay of intermolecular interactions, singlet-triplet energy gap and extent of intersystem crossing using functional group variation. Interestingly, an exciplex assisted ultralong phosphorescence lifetime (more than 20 times) is observed for a combination of triphenylamine and naphthalenemonoimide in air.

10aExciplex10afluorescence10aPhosphorescence10atriphenylamine1 aGoudappagouda1 aAsokan, Kiran1 aNayak, Rashmi1 aKrishnan, Retheesh1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/tuning-phosphorescence-features-triphenylamines-varying-functional-groups-and-intermolecular01589nas a2200181 4500008004100000022001400041245007400055210006900129260000900198300001400207490000700221520098100228100001801209700002601227700002201253700003001275856010201305 2021 eng d a1477-052000aAggregation-induced phosphorescence of an anthraquinone based emitter0 aAggregationinduced phosphorescence of an anthraquinone based emi cFEB  a1004-10080 v193 a

Room temperature phosphorescence (RTP) of metal-free organic molecules is a hot topic of current research interest. RTP can be enhanced through aggregation, crystallization, and the support of polymers and host-guest assemblies. The characteristics of highly phosphorescent aggregates formed from conventional chromophores make them ideal candidates for many potential applications. In this direction, we focused on the aggregation-induced phosphorescence of an anthraquinone derivative AqC6 in solution and in crystal state. The weakly emissive dilute solution exhibits a tunable emission with enhanced intensity and room temperature phosphorescence by increasing the concentration and solvent-antisolvent combination. The enhanced phosphorescence of crystals has been recreated in the solution by making use of aggregation. Interestingly, the support of PMMA enabled AqC6 to achieve enhanced processability, phosphorescence lifetime (174 ms) and quantum yield (5%).

1 aGoudappagouda1 aNidhankar, Aakash, D.1 aNayak, Rashmi, A.1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/aggregation-induced-phosphorescence-anthraquinone-based-emitter01963nas a2200253 4500008004100000022001400041245011500055210006900170260000800239300001400247490000700261520109300268653001501361653001801376653001401394653001801408653002001426100003801446700001801484700002201502700002601524700003001550856012901580 2021 eng d a1867-388000aDurable metalloporphyrin 2D-polymer for photocatalytic hydrogen and oxygen evolution from river and sea waters0 aDurable metalloporphyrin 2Dpolymer for photocatalytic hydrogen a cAPR a1717-17210 v133 a

It is highly imaginary that the outcome of a combination of two complementary resources leads to answer an alarming global issue. One such possible example is the solar seawater splitting for `clean fuel' H-2 generation. Since the catalytic activity and stability of the photocatalysts are substantially challenged in seawater, the design of an efficient and stable photocatalyst is highly desirable. Herein, we demonstrate the solar seawater splitting by a two-dimensional polymer catalyst derived from metalloporphyrin bearing multi-hydroxyl groups. A bimetallic (Co and Ni) porphyrin 2D-polymer exhibits excellent long-term durability of 15 cycles of H-2 and O-2 generation in 200 days from pure water without a considerable decrease in efficiency. Detailed studies using river and seawaters also show the reliable performance of the catalyst over repeated cycles. Here the deactivation modes of catalytic activity have been nullified by the layered metalloporphyrin polymer structure through stable pi-pi stacking, signifying the molecular design of 2D-polymer photocatalyst.

10a2D-polymer10aPhotocatalyst10aporphyrin10aSelf-assembly10awater splitting1 aRanjeesh, Kayaramkodath, Chandran1 aGeorge, Leena1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/durable-metalloporphyrin-2d-polymer-photocatalytic-hydrogen-and-oxygen-evolution-river-and02005nas a2200181 4500008004100000022001400041245006000055210005900115260000800174300001400182490000700196520142700203100002601630700001801656700002501674700003001699856009401729 2021 eng d a2041-652000aEfficient metal-free organic room temperature phosphors0 aEfficient metalfree organic room temperature phosphors cMAR a4216-42360 v123 a

An innovative transformation of organic luminescent materials in recent years has realised the exciting research area of ultralong room-temperature phosphorescence. Here the credit for the advancements goes to the rational design of new organic phosphors. The continuous effort in the area has yielded wide varieties of metal-free organic systems capable of extending the lifetime to several seconds under ambient conditions with high quantum yield and attractive afterglow properties. The various strategies adopted in the past decade to manipulate the fate of triplet excitons suggest a bright future for this class of materials. To analyze the underlying processes in detail, we have chosen high performing organic triplet emitters that utilized the best possible ways to achieve a lifetime above one second along with impressive quantum yield and afterglow properties. Such a case study describing different classes of metal-free organic phosphors and strategies adopted for the efficient management of triplet excitons will stimulate the development of better candidates for futuristic applications. This Perspective discusses the phosphorescence features of single- and multi-component crystalline assemblies, host-guest assemblies, polymers, and polymer-based systems under various classes of molecules. The various applications of the organic phosphors, along with future perspectives, are also highlighted.

1 aNidhankar, Aakash, D.1 aGoudappagouda1 aWakchaure, Vivek, C.1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/efficient-metal-free-organic-room-temperature-phosphors01937nas a2200193 4500008004100000022001400041245012200055210006900177260000800246300001600254490000700270520121800277100003301495700001801528700001501546700002601561700003001587856012601617 2021 eng d a2040-336400aExcimer to exciplex transition through realization of donor-acceptor interactions in luminescent solvent-free liquids0 aExcimer to exciplex transition through realization of donoraccep cJUN a10780-107840 v133 aLuminescent solvent-free organic liquids are known for their enhanced quantum yield, color tunability, and availability of a matrix for other dopants to generate hybrid luminescent materials with improved features for newer applications. Herein, we report a donor-acceptor based luminescent ``exciplex liquid'' by utilizing the slightly different electron affinity of the acceptor molecules. A red-shifted broad exciplex emission exhibited by the donor-acceptor pair even at a lower concentration of the acceptor (0.001 equiv.) indicates high efficiency in the solvent-free state. A detailed NMR study revealed weak intermolecular interactions between the donor and acceptor in the solvent-free matrix that stabilizes the exciplex liquid. The failure of structurally similar solid counterparts to form an exciplex confirms the advantage of the available supportive liquid matrix. Besides, the luminescent exciplex liquid is found efficient in sensing application, which is unachievable by either the individual liquids or their solid counterparts. Here, a transition of a donor-acceptor pair from a solid to solvent-free liquid results in a new hybrid liquid that can be an alternative for solid sensor materials.1 aWakchaure, Vivek, Chandrakan1 aGoudappagouda1 aDas, Tamal1 aRavindranathan, Sapna1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/excimer-exciplex-transition-through-realization-donor-acceptor-interactions-luminescent01604nas a2200229 4500008004100000022001400041245012100055210006900176260000900245300001400254490000700268520078700275100003301062700002101095700002601116700001801142700001801160700001801178700002601196700003001222856012201252 2022 eng d a1359-734500aDonor-acceptor based solvent-free organic liquid hybrids with exciplex emission and room temperature phosphorescence0 aDonoracceptor based solventfree organic liquid hybrids with exci cFEB  a1998-20010 v583 aSolvent-free organic liquids are well-known for their excellent luminescence features. Hence, the recent developments in this area have marked them as potential emitters with high quantum yield and enhanced processability. The support of an available liquid matrix enables doping to deliver hybrid liquids with intriguing luminescence features. In this direction, we report solvent-free liquid donor-acceptor pairs with exciplex emission and room temperature phosphorescence at very low acceptor loading. The underlying weak intermolecular interactions have been revealed by 2D NMR techniques and theoretical calculations. The formation of large-area thin films by exciplex and phosphorescent liquid hybrids will encourage the development of scalable lighting and display materials.1 aWakchaure, Vivek, Chandrakan1 aVeer, Sairam, D.1 aNidhankar, Aakash, D.1 aGoudappagouda1 aNayak, Rashmi1 aAsokan, Kiran1 aRavindranathan, Sapna1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/donor-acceptor-based-solvent-free-organic-liquid-hybrids-exciplex-emission-and-room02004nas a2200241 4500008004100000022001400041245011700055210006900172260000800241300001500249490000600264520116300270653001401433653002001447653001401467653002001481653002501501100002901526700002701555700003001582700002101612856012901633 2022 eng d a2365-654900aHighly efficient and reusable polymer supported palladium catalyst for copper free sonogashira reaction in water0 aHighly efficient and reusable polymer supported palladium cataly cAPR ae2021042730 v73 a

Development of a novel, greener and efficient heterogeneous catalytic system for copper free Sonogashira reaction in water is described. This novel catalyst can be easily prepared by a simple method through synthetic modification of nitrile group in Polyacrylonitrile (PAN) using monoethanolamine (MEA) followed by its complexation with palladium chloride (PdCl2). The resulting polymer Pd complex (mPAN-Pd) was characterized by means of Fourier Transform Infrared Spectroscopy (FTIR), Energy-Dispersive X-ray Spectroscopy (EDAX), Inductively Coupled Mass Spectrometry (ICP-MS) and X-ray Photo Electron Spectroscopy (XPS) analyses. mPAN-Pd was then explored as highly efficient heterogeneous catalyst for Sonogashira coupling reaction under copper and ligand free conditions in water affording the corresponding coupling products up to 97 % isolated yield. Moreover, the catalyst was recovered by simple filtration after the reaction and reused for next 5 cycles with excellent stability and activity. This is the first report on the use of ethanolamine modified PAN Pd (II) complex as an efficient heterogeneous catalyst for a coupling reaction.

10acatalysis10agreen chemistry10aPalladium10aPolymer Support10aSonogashira coupling1 aSruthi, Pambingal, Rajan1 aNimmi, Puthan, Purayil1 aBabu, Sukumaran, Santhosh1 aAnas, Saithalavi uhttp://library.ncl.res.in/content/highly-efficient-and-reusable-polymer-supported-palladium-catalyst-copper-free-sonogashira02375nas a2200217 4500008004100000022001400041245010500055210006900160260000900229300001400238490000700252520160400259100002901863700002001892700002601912700002001938700002201958700002401980700003002004856012302034 2023 eng d a2052-412900aDonor strapped perylene bisimide macrocycle and its lemniscate dimer with extended charge separation0 aDonor strapped perylene bisimide macrocycle and its lemniscate d cOCT  a5099-51070 v103 a

Macrocyclic structures are fascinating due to their unique design and capability to place chromophores in specific orientations, resulting in exciting optoelectronic properties. However, the synthetic challenges limit the broad exploration of such systems. Herein, we report a thiophene-diacetylene-based ring strapped perylene bisimide macrocycle and its notably different electron transfer features. Single-crystal analysis of the macrocycle pointed to the nearly orthogonal placement of donor-acceptor units, facilitating better electronic communication between them. Interestingly, introduction of an alkyl substituent on the peripheral thiophene ring opened the possibility of forming a higher oligomer macrocycle consisting of two strapped perylene bisimide units. Diffusion and two-dimensional NMR experiments provided insight into the structure of the figure-eight-shaped lemniscate dimer. Transient absorption measurements showed faster electron transfer and extended stabilization of the charge-separated state. The thiophene-diacetylene-based ring is a better donor unit to facilitate rapid electron transfer and extended charge separation in the macrocycle and its lemniscate dimer. The new macrocycle design enables the formation of higher analogs equally capable of stabilizing the charge-separated state. Donor-acceptor (D-A) macrocycle designs position the respective units to achieve ultrafast electron transfer precisely and an extended charge-separated state. Here, we report a D-A macrocycle and its lemniscate dimer molecule with exciting electron transfer features.

1 aVeer, Sairam, Dnyaneshwa1 aGoswami, Tanmay1 aRavindranathan, Sapna1 aGonnade, Rajesh1 aKharbanda, Nitika1 aGhosh, Hirendra, N.1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/donor-strapped-perylene-bisimide-macrocycle-and-its-lemniscate-dimer-extended-charge02015nas a2200205 4500008004100000022001400041245010700055210006900162260000900231300001600240490000700256520126800263100002301531700004001554700001801594700001801612700001801630700003001648856013101678 2023 eng d a1144-054600aDonor-acceptor-based two-dimensional polymer as a supercapacitor electrode with long cycling stability0 aDonoracceptorbased twodimensional polymer as a supercapacitor el cOCT  a18049-180540 v473 a

The high demand for energy and energy-storage devices urged organic 2D polymers as a potential candidate in this area. One of the major attractions of 2D polymers in electrochemical applications is their long cycling stability due to their rigid and porous structure. Herein, we developed a 2D polymer comprised of donor-acceptor units exhibiting reasonably good performance as a supercapacitor. The 2D polymer displayed a maximum specific capacitance of 218 F g-1 at a current rate of 0.1 A g-1, a higher power density of 4648.35 W kg-1, and an energy density of 7.05 W h kg-1. In a cycling stability test, it demonstrated a capacitance retention of 70% over 10 000 continuous charge-discharge cycles at a current rate of 2.5 A g-1. Such long cycling stability was attributed to the donor-acceptor units and the crystalline nature of the polymer. The sensible selection of the building blocks of the 2D polymers is crucial for the performance and hence provides scope for improvement. An organic donor-acceptor-based 2D polymer, a promising candidate for energy storage devices, displays a specific capacitance of 218 F g-1, a power density of 4648.35 W kg-1, an energy density of 7.05 W h kg-1, and a capacitance retention of 70% over 10 000 cycles.

1 aBhagyasree, T., M.1 aPuthiyaveetil, Priyanka, Pandinhare1 aKumar, Viksit1 aAsokan, Kiran1 aSreekumar, K.1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/donor-acceptor-based-two-dimensional-polymer-supercapacitor-electrode-long-cycling-stability02131nas a2200301 4500008004100000022001400041245011400055210006900169260000900238490000700247520111200254653001601366653002001382653000901402653002001411653000901431100002901440700001801469700002901487700002401516700002901540700002501569700001801594700002501612700003101637700003001668856013101698 2023 eng d a1861-472800aThermally activated delayed fluorescent solvent-free organic liquid hybrids for tunable emission applications0 aThermally activated delayed fluorescent solventfree organic liqu cJUL 0 v183 a

The synthetic feasibility and excellent luminescence features of organic molecules attracted much attention and were eventually found useful in lighting applications. In this context, a solvent-free organic liquid having attractive thermally activated delayed fluorescence features in bulk along with high processability has prime importance. Herein, we report a series of naphthalene monoimide-based solvent-free organic liquids exhibiting cyan to red thermally activated delayed fluorescence with luminescence quantum yields up to 80% and lifetimes between 10 to 45 mu s. An effective approach explored energy transfer between liquid donors with various emitters exhibiting tunable emission colors, including white. The high processability of liquid emitters improved the compatibility with polylactic acid and was used for developing multicolor emissive objects using 3D printing. Our demonstration of the thermally activated delayed fluorescence liquid will be much appreciated as a processable alternate emissive material suitable for large-area lighting, display, and related applications.

10a3D printing10aEnergy Transfer10aOLED10aOrganic Liquids10aTADF1 aNidhankar, Aakash, D. D.1 aGoudappagouda1 aKothavade, Premkumar, D.1 aDongre, Sangram, D.1 aVeer, Sairam, Dnyaneshwa1 aDash, Soumya, Ranjan1 aRajeev, Kavya1 aUnni, K., N. Narayan1 aShanmuganathan, Kadhiravan1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/thermally-activated-delayed-fluorescent-solvent-free-organic-liquid-hybrids-tunable-emission