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

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