@article {44593, title = {Modulated photochemical reactivities of O-acetylated (3{\textquoteright}, 5{\textquoteright}-dimethoxyphenyl) heteroaryl acyloin derivatives under direct irradiation and photo-induced electron transfer conditions}, journal = {Photochemical \& Photobiological Sciences}, volume = {17}, year = {2018}, month = {JUN }, pages = {835-845}, abstract = {

3{\textquoteright}, 5{\textquoteright}-Dimethoxybenzoin esters are important photoremovable protecting groups which form 2-phenylbenzofuran derivatives upon photo-release. We utilized a similar concept to test a photochemical method of installing a benzofuran moiety to the conjugated backbone by subjecting O-acetylated (3{\textquoteright}, 5{\textquoteright}-dimethylphenyl) heteroaryl acyloin derivatives through direct photo irradiation and a photo-induced electron transfer reaction. These photochemical methods were explored for a variety of heteroaromatic substrates appended on the ketone part of the O-acetylated cross-acyloin derivatives. The furan, thiophene and bithiophene derivatives led to the expected cyclized (benzofuran capped) products but the derivatives with extended conjugation decomposed under direct irradiation. However, under irradiation in the presence of an electron donor such as triethylamine, the extended acyloin derivatives afforded both cyclized and deacetoxylated products. The semiconducting nature of the extended cyclized products was also explored and tested for solution-processed organic field effect transistors, providing a maximum hole mobility of 1.3 x 10(-6) cm(2) V-1 s(-1).

}, issn = {1474-905X}, doi = {10.1039/c8pp00082d}, author = {Bisht, Rajesh and Singh, Saumya and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49137, title = {Modular TiO2-squaraine dyes/electrolyte interface for dye-sensitized solar cells with cobalt electrolyte}, journal = {Chemphotochem}, volume = {7}, year = {2023}, month = {APR}, type = {Article}, abstract = {

Strategies to diminish both charge recombination and aggregation of dyes on the photoanode by functionalizing the sensitizer with alkyl groups is the best approach to achieve high dyesensitized solar cell (DSSC) efficiency. Development of such a photoanode with NIR-active dyes which is compatible with a cobalt electrolyte is important to enhance the photovoltaic performance. In this report, alkyl-group-wrapped donor-acceptor-donor (D-A-D) based unsymmetrical squaraine dyes have been used for DSSC device characterization with a cobalt electrolyte. Surface passivation of photoanode was varied systematically by the extent of functionalization with alkyl groups to avoid charge recombination. DSSC device performance of 5.92\% was achieved for an alkyl-group-wrapped squaraine dye with a cobalt electrolyte. Hence, appending the alkyl groups on the donor unit of squaraine dyes helps passivating the photoanode, whereas introducing hydrophilic groups provides a leaky surface where oxidized electrolyte species reach the titanium-metal-oxide surface which promotes the charge recombination process.

}, keywords = {counter-electrode, DSSC device efficiency, Dye-sensitized solar cells, Electrolytes, unsymmetrical squaraine dye}, issn = {2367-0932}, doi = {10.1002/cptc.202200171}, author = {Singh, Ambarish Kumar and Sudhakar, Vediappan and Javaregowda, Bharathkumar H. and Bisht, Rajesh and Krishnamoorthy, Kothandam and Nithyanandhan, Jayaraj} } @article {49245, title = {MOFite: a high-density lithiophilic and scalable metal-organic framework anode for rechargeable lithium-ion battery}, journal = {ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, volume = {63}, year = {2024}, month = {OCT }, type = {Journal Article}, keywords = {conjugated MOF, Energy storage, lithium ion battery, Metal-organic framework, scalable synthesis}, issn = {1433-7851}, doi = {10.1002/anie.202409256}, author = {Gaber, Safa and Mohammed, Abdul Khayum and Javaregowda, Bharathkumar H. and Martinez, Jose Ignacio and Sanchez, Pilar Pena and Gandara, Felipe and Krishnamoorthy, Kothandam and Shetty, Dinesh} } @article {49848, title = {Mechanochemical large-scale rapid synthesis of ultrapure sodium hexafluorophosphate}, journal = {ChemPlusChem}, volume = {90}, year = {2025}, month = {JUL}, type = {Article}, abstract = {

Among the sodium battery electrolytes, sodium hexafluorophosphate (NaPF6) exhibits superior conductivity, anodic stability, and stable cathode electrolyte interface compared to other electrolytes. Therefore, the synthesis of pure NaPF6 through a simple process is very important. Usually, NaPF6 is synthesized using HF. In our approach, NaPF6 is synthesized by grinding dry ammonium hexafluorophosphate (NH4PF6) and sodium metal. Sodium injects an electron into the ammonium ion, which results in the formation of ammonia and hydrogen. The gram scale synthesis is completed in about 30 min. Purification of the product is not needed. The product purity is confirmed by various spectroscopic and electrochemical techniques. Usually, NaPF6 comprises NaF, HF, and solvents as impurities that affect the performance of SIBs. It has been confirmed that the NaPF6 synthesized by our mechanochemical approach in the absence of solvent is devoid of impurities despite the absence of product purification step. Furthermore, the synthesis of pure NaPF6 (250 g) is demonstrated using a grinder used as household item in cooking Indian pancakes, which costs about 300 USD. The duration of the synthesis of 250 g pure NaPF6 is 1 h. The purity of this sample is comparable to that of NaPF6 (5 g) synthesized using mortar and pestle.

}, keywords = {ammonium hexafluorophosphate, Batteries, carbonates, sodium hexafluorophosphate, sodium vanadium phosphate}, issn = {2192-6506}, doi = {10.1002/cplu.202400640}, author = {Senthilkumaran, Marimuthu and Javaregowda, Bharathkumar H. and Rajendran, Prakash Babu and Balasubramanian, Rajalakshmi and Ajithkumar, Thalasseril G. and Ravindranathan, Sapna and Krishnamoorthy, Kothandam} } @article {49767, title = {Modulation of lithium ion transport and cycling stability using rigid and flexible urethane moieties on the backbone of polymers}, journal = {ACS Applied Materials \& Interfaces}, volume = {17}, year = {2025}, month = {NOV }, pages = {63784-63791}, type = {Article}, abstract = {

Graphite is the anode of choice for lithium-ion batteries. Due to volume change and poor conductivity of inorganic materials, they do not show comparable performance to that of graphite. Conjugated polymers are attractive because of their modularity and ease of synthesis. Herein, we report three polymers based on diketopyrrolopyrrole (DPP) as the anode. In an energy device, stored charges are due to a diffusive and capacitive component. Increasing the capacitive component is a challenge in both organic and inorganic systems. In our polymers, we installed urethane moieties that increase the capacitive component. The excellent Li+ ion transporting urethane moiety is part of the polymer chain. The Li+ ion transport is also impacted by the packing of the polymer chain. Therefore, the DPP units and urethane moieties are connected with either an alkyl chain, phenyl or biphenyl. The polymers with either alkyl or phenyl spacers showed stable cycling stability over 4000 charge-discharge cycles. On the other hand, the specific capacity of the batteries comprising a polymer with biphenyl started decreasing after 500 charge-discharge cycles. This is due to the solubility of the polymer in the battery electrolyte. The polymer with a phenyl spacer showed a higher Li+ ion diffusion coefficient due to the space generated between the polymer chains. The X-ray photoelectron spectroscopy analysis showed that the Li+ ions are bound to carbonyls, indicating the role of urethane in the charge transport. The polymer with an alkyl spacer showed a very high specific capacity of 600 mAh/g (1500th cycle) at a current density of 0.2 A/g, which is much higher than the theoretical capacity of graphite (372 mAh/g). The charge storage in all these polymers is dominated by a capacitive component, with the highest metric of 81\% shown by a polymer with an alkyl spacer.

}, keywords = {Cycling stability, diketopyrrolopyrrole, high capacity, lithium-ion battery, non-conjugatedpolymer, urethane}, issn = {1944-8244}, doi = {10.1021/acsami.5c15080}, author = {Kargude, Radhakisan and Rajendran, Prakash Babu and Kika, Sharmin Percy and Krishnamoorthy, Kothandam} } @article {50020, title = {Metal films from a single source and their application in nanoporous filtration synthesis, electromagnetic interference shielding, and electroadhesion}, journal = {ACS Omega}, volume = {11}, year = {2026}, month = {MAR}, pages = {14203-14211}, type = {Article}, abstract = {

Electroless metal depositions are carried out by a series of reduction steps involving multiple metal ions to obtain a film on synthetic and natural substrates. Herein, we report the use of metal ions from a single element to deposit metal films on various substrates. In a typical metal deposition procedure, Pd2+ ions are anchored on a polycarbonate membrane with vertically aligned pores of 0.6 mu m, which was reduced to its nanoparticles by sodium borohydride. The Pd nanoparticle-modified membrane was then immersed in a Pd plating bath. The Pd2+ ions are reduced by the reducing agent present in the plating bath. The reaction is catalyzed by the Pd nanoparticles. The Pd-modified membrane with vertically aligned Pd tubes were used to convert p-nitrophenol to p-aminophenol, which is an important molecule in the production of acetaminophen. While filtering the reactants through the Pd tubes, due to increased collision between the reactants and the catalyst Pd tubes, 100\% conversion is achieved within 5 min. On the contrary, the conversion is only 10\% if the membrane is placed in a vessel comprising the reactants. Due to the versatile nature of the metal deposition procedure, nickel was deposited on cotton substrates by a similar procedure. The nickel film-coated cotton cloth showed an impressive electromagnetic shielding interference efficiency of -60 dB while the uncoated cotton cloth did not shield electromagnetic radiation. To demonstrate the versatility of the approach, Pd-coated synthetic polymeric substrates are used to electroadhere gels and gel-like substances. Nickel-coated substrates are not suitable for electroadhesion; hence, a conjugated polymer was deposited on the substrate to electroadhere gel-like substances.

}, issn = {2470-1343}, doi = {10.1021/acsomega.4c07730}, author = {Veerasubash, Muthupandi and Birajdar, Sarika Hanamant and Kika, Sharmin Percy and Senthilkumaran, Marimuthu and Deshpande, Karan and Shevate, Rahul and Krishnamoorthy, Kothandam} }