Trends In Chemistry Of Materials: Selected Research Papers of C N R Rao (Iisc Centenary Lecture Series)

"In this collection, the author has compiled a set of his papers representing some of the highlights of materials chemistry. It features a section on oxidic materials, which includes high-temperature superconductivity, colossal magnetoresistance, electronic phase separation and multiferroics. The author has also included novel methods for making gallium nitride, boron nitride and such materials, by using precursors and the urea decomposition route. Moreover, there is a section dealing with open-framework and hybrid materials of which the latter has a great future since one can make use of the rigidity of inorganic structures and the functionality and flexibility of the organic residues to design materials with novel properties."--Jacket CONTENTS......Page 16 Foreword......Page 8 Preface......Page 10 Brief Biography of Professor C.N.R. Rao......Page 12 Acknowledgements......Page 14 I. Some Highlights of Materials Chemistry Commentary......Page 24 Transition metal oxides......Page 26 Superconducting cuprates......Page 28 Colossal magnetoresistance, charge ordering and related properties of rare earth manganates......Page 30 Charge ordering in the manganates......Page 32 Porous solids......Page 33 Molecniar materials......Page 34 Nanomaterials......Page 36 References......Page 37 1. Introduction......Page 40 2. Common reactions encountered in the synthesis of inorganic solids......Page 41 3. Ceramic method......Page 42 5. Precursor method......Page 43 6.1. Dehydration of MOI-x Wx0 3'H20......Page 46 6.2. Reduction ofperovskite oxides......Page 47 7. Intercalation compounds......Page 48 8. Ion exchange method......Page 49 9. Sol-gel method......Page 50 11. Electrochemical method......Page 51 12. High pressure methods......Page 52 14. Intergrowth substrates......Page 54 15. Superconducting cuprates......Page 56 16. Concluding remarks......Page 58 References......Page 59 2. Metal oxides with the perovskite structure......Page 61 3. Cation-deficient perovskites......Page 62 4. Anion-deficient perovskites and vacancy-ordered structures......Page 67 6. Nonstoichiometry in oxides of structures related to perovskites......Page 74 7. Coherent intergrowth phases......Page 75 8. COllcililliillg remarks......Page 78 References......Page 79 4. Intergrowth Structures: The Chemistry of Solid-Solid Interfaces (with J.M. Thomas) Acc. Chem. Res. 18, 113 (1985).......Page 81 Nonrecurrent Intergrowths......Page 83 Recurrent Intergrowths......Page 85 Structure of the Interface......Page 86 Concluding Remarks......Page 87 5. Virtues of Marginally Metallic Oxides Chem. Commun. 2217 (1996).......Page 88 Compositionally controlled metal-insulator transitions in perovskite oxides......Page 89 Perovskite manganates exhibiting GMR......Page 90 References......Page 92 1. Introduction......Page 94 2. Description of electronic charge density......Page 95 3. Charge density from X-ray diffraction......Page 96 4. Data refinement and computer codes......Page 97 S. Theoretical methods......Page 98 6. Charge density in bonds, rings and cages......Page 99 7. Charge density of hydrogen bonds......Page 101 8. Molecular packing in crystals......Page 110 9. Molecular NLO materials......Page 113 References......Page 115 2. Preparation, purification and characterization of fullerenes and fullerene tubules......Page 118 3. Phase transitions in C60 and e 70......Page 119 4. Amorphization of fullerenes under high pressures......Page 127 5. Photoluminescence of Cao under pressure......Page 128 6. Superconductivity in alkali and alkaline earth doped C 60......Page 129 7. Ferromagnetism in C6o.TDAE......Page 133 8. Carbon nanotubes and onions......Page 134 References......Page 135 References......Page 138 General Features of Phase Transitions......Page 140 Polytypism......Page 141 Electronic Transitions......Page 143 Organic Solids and Related Systems......Page 145 Concluding Remarks......Page 146 EXPERIMENT AL......Page 147 RESULTS AND DISCUSSION......Page 148 10. Mechanism of Crystal Structure Transformations: Part 3. Factors Affecting the Anatase - Rutile Transformation (with S.R. Yoganarasimhan) Trans. Faraday. Soc. 58, 1579 (1962).......Page 153 EXPERIMENTAL......Page 154 RESULTS AND DISCUSSION......Page 156 EFFECT OF PARTICLE SIZE ON THE TRANSFORMATION......Page 157 EFFECT OF IMPURITIES ON THE TRANSFORMATION......Page 159 1. Introduction......Page 164 2.1. Molecular Dynamics Methods......Page 165 2.2. Modified Monte Carlo Method......Page 168 2.3. GeneraL Remarks Regarding the MD and Me Methods......Page 170 3.1. Monatomic Solids......Page 171 3.3. Molecular Crystals......Page 172 4. Glasses......Page 178 5. Concluding Remarks......Page 182 References......Page 183 1. Introduction......Page 185 2. Potential models......Page 186 3. Computational details......Page 190 4.1. Solid biphenyl......Page 193 4.2. Structure-potential correlations......Page 198 4.4. The liquid phase......Page 199 References......Page 203 1. Introduction......Page 205 2. Diverse Systems Exhibiting Metal-Nonmetal Transitions......Page 206 3. The Herzfeld Criterion......Page 208 5.1. The Situation in Doped Semiconductors.......Page 209 5.2. The Situation in Transition Metal Oxides.......Page 210 6.1. Criteria for the Transition.......Page 212 6.2. Detailed Models.......Page 213 References and Notes......Page 215 14. Polymerization and Pressure-Induced Amorphization of C60 and C70 (with A. Govindaraj, H.N. Aiyer and R. Seshadri) 1. Phys. Chern. 99, 16814 (1995).......Page 217 References and Notes......Page 218 Results and Discussion......Page 220 References......Page 223 III. Transition Metal Oxides: Superconductivity, Charge-Ordering, Electronic Phase Separation and Multiferroics Commentary......Page 224 References......Page 225 1. INTRODUCTION......Page 226 Electron microscopy......Page 228 Dislocations......Page 230 Domain walls......Page 237 REFERENCES......Page 241 1. Introduction......Page 242 2. Crystal Chemistry......Page 243 3. Infrared Spectra......Page 256 4. Magnetic Properties......Page 257 5. Concluding Remarks......Page 262 References......Page 263 1. Introduction......Page 266 2. Cuprate families......Page 268 4. Electron-superconducting cuprates......Page 278 5. Synthetic aspects......Page 280 6. Commonalities in the cuprates......Page 281 7. Relation between the electronic structure and the superconductivity of cup rates......Page 284 8. Copper-free oxide superconductors......Page 290 10. Concluding remarks......Page 291 References......Page 292 2 Common Structural Features......Page 296 4 Relation between Tc and the In-plane Cu-O Distance......Page 298 5 The Relationship between Tc and the Apical Cu-Q Distance......Page 299 9 The Importance of the Cu-O Charge- Transfer Energy......Page 300 7 References......Page 301 20. Stripes and Superconductivity in Cuprates - Is there a Connection? (with N. Kumar) Chem. Phys. Chem. 4, 439 (2003).......Page 303 Introduction......Page 309 Concluding Remarks......Page 319 References and Notes......Page 320 Introduction......Page 322 Results and Discussion......Page 323 Conclusions......Page 330 1. Introduction......Page 331 2. Electronic orders in rare-earth manganites......Page 332 3. Electronic inhomogeneities in rare-earth manganites......Page 335 4. Electronic phase separation in rare-earth cobaltates......Page 341 5. Theoretical approaches......Page 342 6. Concluding remarks......Page 346 References......Page 347 Introduction......Page 351 Bismuth-based compounds: lone pair effect......Page 354 Rare earth chromites, LnCr03: role of local noncentrosym metry......Page 355 Magnetic ferroelectricity due to charge-ordering......Page 356 References......Page 357 1. Introduction......Page 359 2. Experimental procedure......Page 360 3. Results and discussion......Page 361 References......Page 367 References......Page 370 1. Introduction......Page 372 2. Information Revealed by the Reactions of Organic Amine Phosphates......Page 374 3. Transformations of One-Dimensional Zinc Phosphates......Page 375 5. Transformations of Zero-Dimensional Monomers......Page 377 References......Page 378 1. Introduction......Page 380 2. Stable Organosilanols and Silicate SBUs......Page 381 3. Phosphorus Acids and Phosphate SBUs......Page 384 4. Phosphoric Acid Esters as Primary Building Umts......Page 385 5_ Molecular Phosphate Clusters and Polymers......Page 386 6. Structural Transformations in Metal Dialtyl Phosphates......Page 387 7. Molecular Metal PhospJ1ates from P(O)(OH)3 and Their Conversion to Higher Dimensional Structures......Page 388 References......Page 389 Introduction......Page 392 One-dimensional metal sulfates......Page 393 Two-dimensional metal sulfates......Page 395 Open-framework metal selenites......Page 399 Open-framework metal selenates......Page 402 References......Page 403 Introduction......Page 405 Experimental Section......Page 406 Results and Discussion......Page 408 Conclusions......Page 412 Introduction......Page 413 Experimental Section......Page 414 Results and Discussion......Page 415 Experimental Section......Page 422 Results and Discussion......Page 423 Conclusions......Page 426 Results and discussion......Page 427 Synthesis and characterization......Page 429 References......Page 431 1 Introduction......Page 432 2.2 Coordination polymers......Page 434 2.3 Extended inorganic hybrids......Page 436 2.4 Dense and open frameworks......Page 438 3.1 Effects of ligand geometry and flexibility on dimensionality......Page 439 3.3 Influence of metal ion properties......Page 440 4.1 Effect of reaction temperature and pH......Page 441 4.3 Kinetic vs. thermodynamic factors......Page 442 4.4 Reaction pathways and building-up processes......Page 443 5.2 Catalytic applications......Page 444 5.3 Other applications......Page 445 References......Page 446 2 Experimental......Page 448 3 Results and discussion......Page 449 5 References......Page 451 35. Hydrothermal Synthesis of Organic Channel Structures: 1: 1 Hydrogen-Bonded Adducts of Melamine with Cyanuric and Trithiocyanuric Acids (with A Ranganathan and V.R Pedireddi) 1. Am. Chem. Soc. 121, 1752 (1999).......Page 453 V. Nanomaterials Commentary......Page 456 References......Page 457 Introduction......Page 458 Conclusion......Page 464 Results and Discussion......Page 465 References and Notes......Page 467 Multiwalled and Single-Walled Nanotubes......Page 468 Aligned Carbon Nanotube Bundles......Page 470 V·Junction Carbon Nanotubes......Page 472 Nanorods, l\Iall1llll\llfirg~o;; Materials and Nal'lotubes of Other......Page 473 Properties......Page 475 References......Page 476 1. Introduction......Page 478 3. Nanotubes of Mo and W dichalcogenides......Page 482 4.1. HIS, nanotubes......Page 487 4.5. NbSe, nanotubes......Page 488 6.1. VOx nanotubes......Page 490 6.3. TiO,......Page 492 6.5. Other oxide nanotubes......Page 493 7. N anotubes of BN and other nitrides......Page 494 8. Nanotubes of other materials......Page 497 9. Useful properties of inorganic nanotubes......Page 498 References......Page 499 2.1 Metals......Page 502 2.2 Metal oxides......Page 504 2.3 Metal chalcogenides......Page 506 2.4 Metal pnictides......Page 507 3. Core@shell nanoparticies......Page 509 4.1 Metals......Page 510 4.2 Elemental semiconductors......Page 511 4.3 Metal oxides......Page 512 4.4 Metal cbalcogenides......Page 513 4.5 Metal pnictides and other nanowires......Page 514 4.7 Coaxial cables and other hyhrid nanostructures......Page 515 5. Inerganic nanotubes......Page 516 6. Nanocrystaline films (JPl1lprg,tel1at the liquid-liquid interface......Page 517 References......Page 519 41. Water-Solubilized Aminoc1ay-Metal Nanopartic1e Composites and Their Novel Properties (with K.K.R Datta and M. Eswaramoorthy) J. Mater. Chern. 17,613 (2007).......Page 524 Notes and references......Page 526 Introduction......Page 527 Results and Discussion......Page 528 References and Notes......Page 533 43. Dip-Pen Lithography with Magnetic Fe203 Nanocrystals (with G. Gundiah, N.S. John, PJ. Thomas and G.U. Kulkarni) Appl. Phys. Lett. 84,5341 (2004).......Page 535 44. The Liquid-Liquid Interface as a Medium to Generate Nanocrystalline Films of Inorganic Materials (with K.P. Kalyanikutty) Ace. Chern. Res. 41, 489 (2008).......Page 538 Introduction......Page 539 Gold and Other Metals......Page 540 Metal Chalcogenides......Page 543 Mode of Growth Interface the Films at the......Page 544 Rheological Properties of the Films......Page 546 REFERENCES......Page 547 45. Use of Fluorous Chemistry in the Solubilization and Phase Transfer of Nanocrystals, Nanorods and Nanotubes (with R Voggu, K. Biswas and A. Govindaraj) J. Phys. Chern. B110, 20752 (2006).......Page 549 References and Notes......Page 552 46. Ferromagnetism as a Universal Feature of Nanoparticles of the Otherwise Nonmagnetic Oxides (with A. Sundaresan, R Bhargavi, N. Rangarajan and U. Siddesh) Phys. Rev. B74, 161306(R) (2006).......Page 553 Experimental......Page 557 MoO......Page 559 NiO......Page 560 Conclusions......Page 561 References......Page 562 1. Introduction......Page 563 3. Resnlts and discussion......Page 564 References......Page 566 2. Experimental......Page 567 3. Results and discussion......Page 568 4. Conclusions......Page 570 References......Page 571 50. New Method of Purification of Carbon Nanotubes Based on Hydrogen Treatment (with S.RC. Vivekchand, A Govindaraj and Md. Motin Seikh) J. Phys. Chern. 108,6935 (2004).......Page 572 References and Notes......Page 574 51. Nitrogen- and Boron-Doped Double-Walled Carbon Nanotubes (with L.S. Panchakarla and A Govindaraj) ACS Nano 1, 494 (2007).......Page 575 RESULTS AND DISCUSSION......Page 576 CONCLUSION......Page 579 REFERENCES AND NOTES......Page 580 1. Introduction......Page 582 3.1. Y-junction CNTs......Page 583 3.2. N-doped Y-junction CNTs......Page 585 4. Conclusions......Page 586 References......Page 587 2. Experimental......Page 588 3. Results and discussion......Page 589 References......Page 592 Synthesis......Page 593 3. Results and discussion......Page 594 References......Page 599 55. Functionalization and Solubilization of BN Nanotubes by Interaction with Lewis Bases (with S. Pal, S.R.C. Vivekchand and A Govindaraj) J. Mater. Chern. 17,450 (2007).......Page 601 Notes and references......Page 603 56. GaS and GaSe Nanowalls and Their Transformation to Ga203 and GaN Nanowalls (with u.K. Gautam, S.R.C. Vivekchand and A Govindaraj) Chern. Cornrnun. 3995 (2005).......Page 604 Notes and references......Page 606 1. Introduction......Page 607 4. Theoretical understanding......Page 608 References......Page 609 1. Introduction......Page 611 3.1. Characterization......Page 612 3.2. Mechanical properties......Page 613 3.3. Fractographic observations......Page 614 4.1. Stiffness......Page 615 5. Summary......Page 616 References......Page 617 2. Experimental details......Page 618 3. Results and discussion......Page 619 References......Page 625 Experimental......Page 627 Characterization......Page 628 Gas adsorption......Page 630 Electrochemistry......Page 631 Functionalization and solubilization......Page 632 References......Page 633 This reprint volume arises from the Centenary Lectures at the Indian Institute of Science, initiated to mark the beginning of the 100th year of the institution. C N R Rao (b.1934), director of the institution 1984-1994, and pioneering solid state chemist, was the first lecturer. He provides a preface to this selection of his papers stating that his intent was to represent some highlights of materials chemistry and some current work, although he specifies that new results were coming out of the laboratory even as the book went to press. His career has spanned 50 years; of the articles presented here, reprinted from various journals (e.g. J. Materials Chemistry, Indian J. Chemistry, J. of Molecular Structures, among others), the oldest is from 1962, and more than half are from the past few years (2004 through 2008). Arrangement of the 60 articles is in sections (with introductions by Rao) on highlights of the field, transition metal oxides, open-framework and hybrid network materials, and nanomaterials. There is no index. Annotation 2008 Book News, Inc., Portland, OR (booknews.com)