Department of Chemistry

Indian Institute of Technology Hyderabad (IITH) is a premier institute of science and technology established in 2008. IITH has been consistently ranked in the&nbsp;<a href="https://iith.ac.in/reports/" rel="noopener noreferrer">top 10 institutes</a>&nbsp;in India for Engineering&nbsp;<a href="https://www.nirfindia.org/2021/EngineeringRanking.html" rel="noopener noreferrer" target="_blank">according to NIRF</a>&nbsp;making it one of the most coveted schools for science and technology in the country.

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The very foundation of IIT Hyderabad is based on&nbsp;<a href="https://iith.ac.in/research/">research and innovation</a>. The vibrant research culture is evident from the number of patents and publications that IITH produces consistently every year. IITH offers&nbsp;<a href="https://iith.ac.in/academics/programmes-offered/">graduate programs</a>&nbsp;at both a masters, and a doctoral level, in several diverse areas. There are separate programs for technology, design, science, and liberal arts. The&nbsp;<a href="https://iith.ac.in/academics/post-graduate/">MTech program</a>&nbsp;is offered in various modes and durations to cater to the ever-growing need of postgraduate level professionals in the country.

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IITH creates a unique holistic ecosystem for education that offers interactive learning, a very flexible academic structure, cutting-edge research, strong industry collaboration, and entrepreneurship. This is an environment which enables students and faculty to translate their dreams into realities.

IIT Hyderabad

LiMnPO4 nanoparticles synthesized by the polyol method were examined as a cathode material for advanced Li-ion batteries. The structure, surface morphology, and performance were characterized by X-ray diffraction, high resolution scanning electron microscopy, high resolution transmission electron microscopy, Raman, Fourier transform IR, and photoelectron spectroscopies, and standard electrochemical techniques. A stable reversible capacity up to 145 mAh g-1 could be measured at discharge potentials >4 V vs Li/ Li+, with a reasonable capacity retention during prolonged charge/discharge cycling. The rate capability of the LiMnPO4 electrodes studied herein was higher than that of LiNi0.5 Mn0.5 O2 and LiNi0.8 Co0.15 Al0.05 O2 (NCA) in similar experiments and measurements. The active mass studied herein seems to be the least surface reactive in alkyl carbonate/ LiPF6 solutions. We attribute the low surface activity of this material, compared to the lithiated transition-metal oxides that are examined and used as cathode materials for Li-ion batteries, to the relatively low basicity and nucleophilicity of the oxygen atoms in the olivine compounds. The thermal stability of the LiMnPO4 material in solutions (measured by differential scanning calorimetry) is much higher compared to that of transition-metal oxide cathodes. This is demonstrated herein by a comparison with NCA electrodes. © 2009 The Electrochemical Society.

World University root node

Journal of the Electrochemical Society

LiMnPO4 as an advanced cathode material for rechargeable lithium batteries

A novel hybrid of azacrown ether-oxabridged fluorogenic chemosensor (L1) has been synthesized: the metal ion binding ability of the hybrid molecule shows higher affinity towards transition metal ion Zn2+ and heavy metal ion Hg2+ compared to the parent azacrown ether which shows poor metal ion selectivity: the binding modes of the Zn2+ and Na+ towards L1 have been discussed. © The Royal Society of Chemistry 2009.

Chemical Communications

Azacrown-oxabridged macrocycle: A novel hybrid fluorogenic chemosensor for transition and heavy metal ions

A simple protocol for the synthesis of an aesthetically pleasing 'oxa-basket' (5-methoxy-2,8,13-trioxapentacyclo[7.2.1.1.5,120.4,1106,10]tridecane-3,7-dione), possessing 9-oxa-noradamantane core, is described. The readily available diquinane based dichloro bis-γ-lactone precursor upon treatment with MeSO3H furnished dichloro 'oxa-basket' which was dechlorinated using TBTH/AIBN to obtain the title compound. The key role of the chlorines was demonstrated by replacement with hydrogen or allyl substituents which redirects the cascade to simple hydrolysis products. © 2009 Elsevier Ltd. All rights reserved.

Tetrahedron Letters

Synthesis of 9-oxa-noradamantane derivative, an aesthetically pleasing 'oxa-basket'

Novel norbornyl-ferrocene hybrids have been synthesized in excellent yields via Diels-Alder reactions between 1,2,3,4-tetrahalo-5,5- dimethoxycyclopentadiene and vinyl-or acryloylferrocenes. Halogen reduction of vinylferrocene adducts followed by catalytic hydrogenation afforded ferrocenyl-norbornane. Hybrids showed the dependence of the redox potential on the nature of the substituents on the norbornyl moiety. © Georg Thieme Verlag Stuttgart.

Synthesis

Synthesis and electrochemical signature of novel norbornyl-ferrocene hybrids

Bismuth goes GaGa: Dibismuthenes are derived from commercially available bismuth(III) triflate or aryloxide salts by employing [Ga(ddp)] (ddp=CH[MeC(2,6-iPr2C6H3)N]2) as an efficient reducing agent and trapping ligand. Apart from the shortest bismuth-bismuth bonds known to date, the compounds demonstrate the unique synthetic potential in main-group chemistry of lowcoordinate Group 13 compounds analogous to N-heterocyclic carbenes. © 2009 Wiley-VCH Verlag GmbH &amp; Co. KGaA.

Angewandte Chemie - International Edition

A short Bi=Bi bond supported by a metalloid group 13 ligand

A series of blue-emitting phosphor Sr3-xEuxAl10SiO20 (x=0-0.025, insteps of 0.0025) have been synthesized and the emission intensity is found to be maximum for x=0.02. The effect of boron substitution in the Al site in Sr3Al10SiO20:Eu2+ phosphor has been investigated to improve the blue emission of Eu2+. A series of boron-substituted compositions have been made Sr2.979Eu0.021Al10-xB xSiO20 (x=0, 0.25, 0.5, 0.75 and 1) and studied their photoluminescence (PL) property under UV and VUV excitation. The X-ray diffraction patterns of Sr2.979Eu0.021Al10-xB xSiO20 (x=0, 0.25, 0.5, 0.75 and 1) show single phase formation and all the compositions crystallize in monoclinic structure with space group C2/m. Blue emission (due to Eu2+ion) has been found in all compositions and the emission intensity is found to be maximum for x=0.25 and it is ∼2 times higher than that of x=0 composition (PL intensity 62% vs. commercial BAM). Hence, this phosphor could be possible potential candidate for blue light-emitting phosphor for plasma display panel (PDP) applications. © 2009 Elsevier B.V. All rights reserved.

Journal of Luminescence

Novel blue-emitting phosphor Sr2.979Eu0.021Al10-xB xSiO20 (x=0, 0.25, 0.5, 0.75 and 1) for PDP applications

Reactions of M(CH2Ph)4 (M = Zr, Hf) with various α-diimine ligands afforded amido-imino or diamido complexes through intramolecular benzylation of the C=N bonds of the ligands. Selective benzylation of a-diimine ligands, i.e., single- and double-benzylation, was accomplished by varying the substituent on the nitrogen atom of the imine moiety or the ligand backbone. Kinetic analysis of the second benzylation step indicated that the benzyl group migrated from the metal center to the C=N moiety via an ordered four-center transition state (ΔS‡ ≈ -3(4) eu for 3a; -5(9) eu for 5b). Upon activation with B(C6F 5)3 or [Ph3C][B(C6F5)4], amido-imino (3, 6) and diamido (2, 4) complexes became active catalysts for 1-hexene polymerization, and the resulting poly(l-hexene)s had moderate isotacticity ([mmmm], up to 90%). Polymerization of vinylcyclohexane was also catalyzed with moderate activity to give highly isotactic poly(vinylcyclohexane) ([mmmm] &gt; 95%) via a chain-end control mechanism. © 2009 American Chemical Society.

Organometallics

Controlled benzylation of α-diimine ligands bound to zirconium and hafnium: An alternative method for preparing mono- and bis(amido)M(CH 2Ph)n (n = 2, 3) complexes as catalyst precursors for isospecific polymerization of α-olefins

The reactions of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im DippNH, 1-H) with trimethylsilylmethyl lithium (LiCH 2SiMe3) and anhydrous rare earth metal trichlorides MCI3 afforded the imidazolin-2-iminato complexes [(1)MCI 2(THF)3] (2a, M = Sc; 2b, M = Y.; 2c, M = Lu) and [(1)GdCI2(THF)2]·[LiCI(THF)2] (2d). Treatment of complexes 2 with dipotassium cyclooctatetradienide, K 2(C8H8) resulted in the formation of two- or three-legged pianostool complexes of the type [(η8-C 8H8)M(1)(THF)n] (3a, M = Sc, n = 1; 3b, M = Y, n = 2; 3c, M = Lu, n = 2; 3d, M = Gd, n = 2). X-ray diffraction analyses of all eight complexes 2 and 3 revealed the presence of very short metal-nitrogen bonds, which are among the shortest ever observed for these elements. [(η8-C8H8)Sc(1)(THF)] (3a) reacted with 2,6-dimethylphenyl isothiocyanate (Xy-NCS) to form the [2 + 2]-cycloaddition product 4, which contains a thioureato-N,N′ moiety. The related COT-titanium complex [(η8-C8H8)TiCI(1)] (6) could be obtained from [(1)TiCI3] (5) by reaction with K 2(C8H8) and was structurally characterized. As a theoretical analysis of the nature of the metal-nitrogen bond, density functional theory (DFT) calculations have been carried out for complexes 3a and 6 and also for the model complexes [(η8-C8H 8)Sc(NlmMe)] (7), [(η8-e8H 8)Ti(NlmMe)]+ (8), and [(η8- C8H8)Ti (NXy)] (9), revealing a marked similarity of the bonding in imidazolin-2-iminato and conventional imido metal complexes. © 2009 American Chemical Society.

Inorganic Chemistry

Imidazolin-2-iminato complexes of rare earth metals with very short metal-nitrogen bonds: Experimental and theoretical studies

Bis(phosphinimino)methanides exhibit a wide variety of coordination chemistry with almost all elements in the periodic table. This critical review deals with the chemistry and coordination behavior of bulky monoanionic (CH(PPh2NR)2)−bis(phosphinimino)methanide and dianionic (C(PPh2NR)2)2−bis(phosphinimino)methanediide (R = SiMe3, aryl) ligands focusing on s- and p-block as well as transition metals (109 references). © 2009 The Royal Society of Chemistry.

Chemical Society Reviews

Main-group and transition-metal complexes of bis(phosphinimino)methanides

Pure phases of a new oxyarsenide superconductor of the nominal composition CeFe0.9Co0.1AsO were successfully synthesized by solid state reaction in sealed silica ampoules at 1180 {ring operator}C. It crystallizes in the layered tetragonal ZrCuSiAs type structure (sp gp P 4 / n m m) with lattice parameter of ' a ' = 3.9918 (5) Å and ' c ' = 8.603 (1) Å. A sharp superconducting transition is observed at 11.31 K (± 0.05 K) with an upper critical field of 45.22 T at ambient pressure. The superconducting transition temperature is drastically lowered (∼ 4.5, 4.9 K) on increasing the concentration (x = 0.15, 0.2) of cobalt. © 2008 Elsevier Ltd. All rights reserved.