01876nas a2200397 4500008004100000245007700041210006900118260000800187520046300195100002900658700002900687700003000716700001900746700004300765700003000808700002400838700002000862700002700882700002900909700003100938700001900969700003200988700003101020700002901051700002501080700003001105700002801135700003101163700002401194700003001218700003401248700003101282700003301313700002501346856010701371 2012 eng d00aEthyl oligo-silicates with strong acid heterogeneous polymeric catalysts0 aEthyl oligosilicates with strong acid heterogeneous polymeric ca cMAY3 a

The present invention provides a process for the synthesis of ethyl silicate with varying silica concentration, by hydrolysing ethyl silicate in varying water concentration in the presence of sulfonated catalysts having a styrene-divinyl benzene backbone. The present invention further relates to the preparation of beaded crosslinked polymers containing sulfonic acid moieties having an interconnected pore structure and surface area up to 400 m2 /g.

1 aBevara, Madhusudana, Rao1 aBhongale, Sunil, Sitaram1 aBhosle, Sonali, Madhavrao1 aChavan, Nayaku1 aChelanattukizhakkemadath, Raman, Rajan1 aDeokar, Sarika, Babasaheb1 aDhoble, Deepa, Arun1 aDwivedi, Mayank1 aGhorpade, Ravindra, V.1 aHarikrishna, Reghunathan1 aDhanasekharan, Janakiraman1 aJohn, Aruldoss1 aLocanindi, Hari, Sarvothama1 aMomin, Mohasin, Shamshuddi1 aMulani, Khudbudin, Baban1 aMule, Smita, Atmaram1 aNalawade, Archana, Chetan1 aPunitharasu, Vellimalai1 aQureshi, Mohammed, Shadbar1 aKumar, Tayal, Rajiv1 aShaikh, Wasif, Abdul Late1 aSontakke, Kalpana, Vishwanath1 aReddy, Krishna, Mohan Srin1 aSriperambudur, Rajesh, Kumar1 aPonrathnam, Surendra uhttps://library.ncl.res.in/content/ethyl-oligo-silicates-strong-acid-heterogeneous-polymeric-catalysts02883nas a2200241 4500008004100000022001400041245023400055210006900289260000800358300001600366490000600382520186700388653002502255653003002280653003002310653002402340653003002364653002802394100002802422700003902450700002702489856012502516 2017 eng d a1944-824400aInterplay between pi-bridges and positions of branched alkyl groups of unsymmetrical D-A-D-pi-A squaraines in dye-sensitized solar cells: mode of dye anchoring and the charge transfer process at the TiO2/Dye/electrolyte interface0 aInterplay between pibridges and positions of branched alkyl grou cSEP a32698-327120 v93 a

Far-red-absorbing squaraines possessing high molar absorptivity (>10(5) M-1 cm(-1)) are being attracted as high-efficiency chromophores in dye-sensitized solar cells (DSSCs). A series of donor acceptor -donor-pi spacer-acceptor (D-A-D-pi-A) unsymmetrical squaraines, PSQ1-5, with indoline donor and squaric/cyanoacetic acid acceptor units, were designed for sensitized solar cells. For extending the absorption toward the near-infrared region (NIR) and controlling the orientation on the TiO2 surface, benzene (PSQ1 and PSQ2) and thiophene (PSQ3-5) 7r-spacers and out-of-plane branched alkyl groups at the indoline that are away (PSQ1, PSQ3, and PSQS) or near (PSQ2 and PSQ4) the anchoring group, respectively, were introduced. Dynamic aggregation tendency of PSQ1 and PSQ3 than that of their isomers systematically modulates the orientation on the TiO2 surface, which in turn enhances photovoltaic performance. Absorptance on a thin transparent TiO2 film shows a visible-to-NIR response with an onset around 800 nm for PSQ3-5. Although there is resemblance in electrochemical redox levels, their high injection efficiency and recombination resistance differentiated impact on the way of anchoring and the dihedral angle between D-A-D units and g-spacers. DSSCs sensitized with PSQS achieved a PCE of 8.15% under simulated AM 1.5G illumination (100 mW cm(-2)), with the current density (j) and open-circuit voltage (Voc) of 19.73 mA cm(-2) and 630 mV, respectively. A clear comparison of the incident-photon-to-current conversion efficiency versus the light-harvesting efficiency correlates the structure-property relationship with J obtained for PSQ dyes. Electrochemical impedance spectroscopy was carried out to examine the TiO2/dye/electrolyte interface for further confirmation of the enhanced PCE of top-se-alkylated PSQS over that of other dyes.

10aD-A-D-pi-A framework10adye-sensitized solar cell10aH- and J-type aggregation10aorientation of dyes10astatic/dynamic aggregates10aunsymmetrical squaraine1 aPunitharasu, Vellimalai1 aKavungathodi, Munavvar, Fairoos Me1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/interplay-between-pi-bridges-and-positions-branched-alkyl-groups-unsymmetrical-d-d-pi02605nas a2200181 4500008004100000245018600041210006900227260000800296300001600304490000600320520182500326100002402151700002402175700003902199700002802238700002702266856013002293 2017 eng d00aOrthogonally functionalized donor/acceptor homo- and heterodimeric dyes for dye-sensitized solar cells: an approach to introduce panchromaticity and control the charge recombination0 aOrthogonally functionalized donoracceptor homo and heterodimeric cOCT a34875-348900 v93 aOrganic dyes possessing conjugated pi-framework forms closely packed monolayers on photoanode in dye-sensitized solar cell (DSSC), because of the limitation to control the orientation and the extend of intermolecular pi-pi interaction, self-aggregation of dyes leads to reduced cell performance. In this report, a series of homodimeric (D-1-D-1, and D-2,-D-2) and heterodimeric (D-1-D-2 and D-2-D-4) donor/acceptor (D/A) dyes containing spiroBiProDOT pi-spacer were designed and synthesized by utilizing Pd-catalyzed direct arylation reaction and correlates the device performance with monomeric dyes (D-1 and D-2). Both the thiophenes (pi-spacer) of spiroBiProDOT were functionalized with same or different donor groups which led to homodimeric and heterodimeric chromophores in a single sensitizer. The homodimeric spirodye D-1-D-1 showed higher power conversion efficiency (PCE), of 7.6% with a V-oc and J(sc) of 0.672 V and 16.16 mA/cm(2), respectively. On the other hand, the monomeric D-1 exhibited a PCE of 3.2% (V-oc of 0.64 V and J(sc) of 7.2 mA/cm(2)); which is lower by 2.4 fold compared to dimeric analogue. The spiro-unit 20 provides flexibility between the incorporated chromophores to orient on TiO2 due to four sp(3)-centers, which arrest the molecular motions after chemisorption. This study shows a new molecular approach to incorporate two chromophores in the dimeric dye possessing complementary absorption characteristics toward panchromatic absorption. The attenuated charge recombination at TiO2/Dye/redox couple interface in case of D-1-D-1, owing to better passivation of TiO2 surface, was elucidated through impedance analysis. The FT-IR spectrum of D,-D, adsorbed on TiO2 film indicated both the carboxylic units were involved in chemisorption which makes strong coupling between dye and TiO2.1 aSil, Manik, Chandra1 aSudhakar, Vediappan1 aKavungathodi, Munavvar, Fairoos Me1 aPunitharasu, Vellimalai1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/orthogonally-functionalized-donoracceptor-homo-and-heterodimeric-dyes-dye-sensitized-solar02134nas a2200157 4500008004100000245012900041210006900170260000800239300001600247490000700263520148600270100002801756700003901784700002701823856012601850 2018 eng d00aSelf-assembly of Cis-configured squaraine dyes at the TiO2-dye interface: far-red active dyes for dye-sensitized solar cells0 aSelfassembly of Cisconfigured squaraine dyes at the TiO2dye inte cMAY a16541-165510 v103 aTo synergize both steric and electronic factors in designing the dyes for dye-sensitized solar cells, a series of cis-configured unsymmetrical squaraine dyes P11-P15 with suitably functionalized alkyl groups and squaric acid units containing the electron-withdrawing groups were synthesized, respectively. These dyes capture the importance of (i) the effect and position of branched alkyl groups, (ii) mono- and di-anchoring groups containing dyes, and (iii) further appending the alkyl groups through the cyanoester vinyl unit on the central squaric acid units of DAD-based cis-configured squaraine dyes. All the above factors govern the controlled self-assembly of the dyes on the TiO2 surface which helps to broaden the absorption profile of the dyes with an increased energy-harvesting process. With respect to the position of the branched alkyl groups, dye P11 with the sp(3)-C and N-alkyl groups away from the TiO2 surface showed a better device efficiency of 5.98% (J(sc) of 14.46 mA cm(-2), V-oc of 0.576 V, and ff of 71.8%) than its positional isomer P12 with 3.45% (J(sc) of 8.78 mA cm(-2), V-oc of 0.554 V, and ff of 70.9%). However, with respect to the dyes containing mono- and di-anchoring groups, P13 with two anchoring units exhibited a superior device performance of 7.58% (J(sc) of 17.12 mA cm(-2), V-oc of 0.618 V, and ff of 71.7%) in the presence of optically transparent co-adsorbent CDCA (3 alpha,7 alpha-dihydroxy-5 beta-cholanic acid) than dyes P11 and P12.1 aPunitharasu, Vellimalai1 aKavungathodi, Munavvar, Fairoos Me1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/self-assembly-cis-configured-squaraine-dyes-tio2-dye-interface-far-red-active-dyes-dye02335nas a2200241 4500008004100000022001400041245011500055210006900170260000800239300001400247490000600261520145000267653002301717653002001740653003101760653003201791653002601823100002801849700003901877700002701916700002701943856012301970 2019 eng d a2574-096200api-Extended cis-configured unsynimetrical squaraine dyes for dye-sensitized solar cells: panchromatic response0 apiExtended cisconfigured unsynimetrical squaraine dyes for dyese cDEC a8464-84720 v23 a

{Light absorbing sensitizer is the heart of the third generation photovoltaic technologies such as dye sensitized solar cells. Despite possessing large extinction coefficients for the metal-free organic dyes, the light harvesting efficiency is limited with the narrow absorption 20 profile in either visible or NIR regions of the solar spectrum. Though monolayer formation of organic sensitizers on semiconducting metal oxide surface leads to dye-dye interaction that leads to broadening the absorption profile, the contribution of the aggregated state to the power conversion process is found out to be poor. Here, we have engineered far-red active pi-extended cis-configured unsymmetrical squaraine dyes with carboxylic acid and cycnoacetic acid as anchoring groups with controlled aggregation and panchromatic light absorption by including the steric and electronic factors. The presence of sp(3)-C (out-of-plane) and N-alkyl (in-plane) groups played an important role in modulating the assembly of the dyes on the TiO2 electrode; the cis-squaraine unit helps to extend the conjugation in the NIR region besides enhancing the visible transition and the incident photon-to-current conversion efficiency profile that showed the importance of anchoring groups for the panchromatic response. Dye PSQ10 showed solar-to electric conversion with an onset of 850 nm with the device performance of 7.0% (V-oc = 0.581 V, J(sc) = 17.06 mA/cm(2)

10acis-squaraine dyes10aDye aggregation10aDye-sensitized solar cells10aextended far-red absorption10apanchromatic response1 aPunitharasu, Vellimalai1 aKavungathodi, Munavvar, Fairoos Me1 aSingh, Ambarish, Kumar1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/pi-extended-cis-configured-unsynimetrical-squaraine-dyes-dye-sensitized-solar-cells