Affiliation Index

428

SUPRAMOLECULAR ARCHITECTURE Switzer, Jay Α., 244 Tarasevich, Barbara J., 61 Thompson, J. D., 33 Thompson, Mark E., 166 Treece, Randolph E., 369 Ungashe, S., 24 Vichi,EduardoJ.S.,314

Ward, Michael D., 231 Webber, S. E.,405 Whitesides, George M . , 10 Wiley, John B., 369 Wu, C.-G., 194 Yonemoto, Edward H., 333 Zerkowski, Jonathan Α., 10

Downloaded by 5.189.136.214 on May 5, 2018 | https://pubs.acs.org Publication Date: July 14, 1992 | doi: 10.1021/bk-1992-0499.ix002

Affiliation Index AT&T Bell Laboratories, 24 Argonne National Laboratory, 155 Centre National de la Recherche Scientifique, 88,114,220 Colorado State University, 76 Harvard University, 10 Hebrew University of Jerusalem, 384 Los Alamos National Laboratory, 33 Michigan State University, 145,194 Middle East Technical University, 314 New Mexico State University, 46 Northwestern University, 194 Pacific Northwest Laboratory, 61

Princeton University, 166 Purdue University, 1,274 Texas A & M University, 128,178 Universidade Estadual de Campinas, 314 University of California—Los Angeles, 369 University of California—Santa Barbara, 294 University of Melbourne, 256 University of Minnesota, 231 University of Missouri—Rolla, 244 University of Oregon, 355 University of Texas at Austin, 333,405 University of Texas at Dallas, 347 University of Toronto, 314

: Index A Amorphous networks, 4-5 Amorphous solid synthesis via ultrathinfilm multilayer composites analysis of solid-state reaction mechanisms, 357,358/ application to synthesis of metastable ternary compounds, 366 control of crystallization of amorphous alloy, 360,363,365-367/ control of formation of homogeneous amorphous alloy, 360,361-362/ differential scanning calorimetric procedure, 359-360 grazing measurement procedure, 359 togh-angle XRD procedure, 359 length scales vs. course of solid-state reactions, 360,361-362/363 quantitative analysis of interdiffusion reaction, 356-357

Amorphous solid synthesis via ultrathinfilm multilayer composites—Continued stoichiometry vs. mechanism of solid-state reaction, 363,364-366/ synthetic procedure for modulated composites, 359 Aniline, intercalation in layered protonic conductors, 220-229 Aromatic polycyclic molecules, use as probe molecules for mechanistic studies of sol-gel-xerogel transitions and cage properties, 400 Artificially layered ceramics, nanoscale, electrodeposition, 244-253 Asymmetrically layered zirconium phosphonates, 166-176 experimental procedure, 174-176 interlayer spacings of compounds, 170i schematic representations of layers, 169/ synthesis, 167-168 synthesis of acyl chloride derivatives, 169-170

Bein; Supramolecular Architecture ACS Symposium Series; American Chemical Society: Washington, DC, 1992.

INDEX

429

Asymmetrically layered zirconium phosphorates—Continued Zr-COOH-H, 171-172,173/,174 Zr-COOH-OH, 170-171,173/,174 Au (111) substrate, modification using highcurrent scanning tunneling microscopic techniques, 77


Β Barbituric acid, structure, 16 Bioactive glasses additives vs. activity, 392 complex formation with Coomassie blue, 393-394 diffusion of protein within glass matrix, 391-392 entrapment technique, 391-393 forms of enzyme, 393 inactivation of cell-free enzyme, 392 protective effect of immobilization matrix against thermal inactivation, 394 Biological hard tissues, 61-62 Biomimetic thin-film synthesis, 61-75 development times vs. film growth, 72,73/ experimental procedure, 64,67 polyethylene derivatization scheme, 64,65/ self-assembled monolayer derivatization scheme, 64,66/67 SEM of iron oxide deposited on sulfonated polystyrene, 68,7Qf sulfonate site density vs. iron oxide deposition, 68,71/ surface hydrophobicity vs. film density, 68,72 surface vs. electron micrographs, 68,6Sy use of derivatized self-assembled monolayers, 67 use of polyethylene, 67 Biomineralization applicability to mineral deposition not found in nature, 62 features important to materials science, 62 mechanism, 61-62 possible mechanisms of film growth, 62-63,65/ N^'-Bis(3-cMorophenyl)melaminebarbital complex, sheet packing, 20,21/

yV^'-Bis(4-chlorophenyl)melaminebarbital complex, sheet packing, 19f WJV'-Bis(4-memylphenyl)melaminebarbital complex, sheet packing, 20f

C Cacoxenite, three-dimensional periodic packaging, 309 Catalytic metal and oxide particles, trapping in sol-gel glasses, 390 Cationic intercalation chemistry, reactions, 102 Ceramics, artificially layered nanoscale, electrodeposition, 244-253 Chemical methods using STM for surface modification, 78,80 Chemical reactivity, low-dimensional solids, soft chemistry routes to new solids, 88-112 Chemical sensors from sol-gel glasses, mechanism of reagent trapping and exposure, 389-390 Chemically reactive organically doped sol-gel glasses chemical sensors, 389-390 photoreactive sol-gel glasses, 386-389 Chemie douce, approach to control of intermediates in solid-state syntheses, 356 Clays structure vs. applications, 155 use as petroleum cracking catalysts, 128 Ousters, zeolite inclusion chemistry, 274-292 Complex assemblies of functional groups in ordered organic films, 2-3 Conductive polymers, crystalline inorganic hosts as media for synthesis, 195-217 Copolymerization, sol-gel glasses, 401 Copper, adsorption of self-assembled monolayers, 14-15 Covalently linked donor-acceptor molecules, effect on kinetics of electron-transfer reactions in zeolites, 338-344 Critical length scale, definition, 363 Crystal chemistry of low-dimensional solids band scheme models for transition-metal chalcogenides, 90,91/92 intrinsic instability effect, 89



430

SUPRAMOLECULAR ARCHITECTURE

Crystal chemistry of low-dimensional solids—Continued ions vs. stability, 89-90 strength of bonding through interslab or interfiber spacings, 89 Crystal engineering of materials composed of infinite frameworks, 256-272 cavities and channels, 257 diamond-related frameworks, 258,259-26Qf,261 future research, 269,273 honeycomb net, 261,262-263/ interpénétration, 257 interpénétration of square grid sheets to form novel three-dimensional network, 261,264-265/266 PtS-related frameworks, 269,270-272/" rutile-related frameworks, 266,267/ three-dimensional net with four connected porphyrin building blocks, 266,268/269 Crystal growth rates, determination, 236-242 Crystalline hosts as media for conductive polymer synthesis, 194-218 charge-transport properties of polyaniline-FeOQ, 210,212-213/ charge-transport properties of polyaniline in N K C N ) ^ , 214^16/217 charge-transport properties of polyturan-FeOa, 214,215/ charge-transport properties of polypyrrole in N i ( C ^ N ^ , 214,216/217 continuing polymerization of polyaniline, 202-203 experimental materials, 195 FeOQ as intercalation host, 196,197/ Fourier transform IR spectra of polyfuran-FeOa, 204,205/ Η - a bonding between FeOQ layers, 202 insertion of polyfuran in FeOQ, 203,204^05-206/ location of polymer chains, 217 orientation of polyaniline chains with respect to FeOQ lattice, 198,201/202 oscillation photographs of a-(r^lyaniline) êOQ, 198,20Qf physical measurement procedure, 196 polyaniline insertion in single-crystal FeOQ, 195-196,198-202

Crystalline hosts as media for conductive polymer synthesis—Continued polymerization in Hormann-type inclusion compounds, 204,207-211 proposed structure of polyaniline, 198 reaction of NKC^jNHâniline) with Fe* 196 reaction of NiiO^NHgteyrrole) with Fe *, 195-196 reaction of tetrafuran with FeOQ, 195 removal of Ni(CN) NH host, 196 selected area diffraction pattern of polyfuran-FeOQ crystallites, 204,206/ SEM of a-(polyaniline) FeOQ, 196,198,199/ Crystalline products, synthesis via metastable amorphous intermediates, 355-367 Crystalline substructures, hydrogen-bonded networks, 16-17,18/ 3

2

3

x

D Deposition of electron donors, acceptors, and insulators as components of zirconium diphosphonate multilayer films, 24-32 Design low-dimensional solids, soft chemistry routes to new solids, 88-112 ordered molecular arrays in two and three dimensions, 10-22 Diamond-related infinite frameworks adamantane-like unit, 258,259/" interpénétration, 258^6Q^261 structure, 258,259/ l,4-Diazabicyclo[2.2.2]octane, threedimensional periodic packaging, 309 Differential scanning calorimetry, advantages for solid-state reaction studies, 357 2^-Dimethyldicyanoquinonediimine polymerization with ruthenium, 38,41-44 structure, 38 Diodes, use of thin films, 3 Diphosphate esters, basal spacing, 183/184 Dye laser materials, 397-398 Ε

0

Electrochemical parameters, role in electrocrystallization of lowdimensional molecular solids, 234-235


431


INDEX Electrocrystallization of low-dimensional molecular solids, 231-242 crystal growth at 10-μπι diameter microelectrode, 237,24Qf,241 crystal growth rate determination, 236-242 current transitions vs. potential, 237,239f electrochemical parameters vs. morphology, 236 elementary steps, 232,233/234 experimental procedure, 241,243 frequency response vs. crystal growth rate, 237,238/ growth of low-temperature superconductor, 241,242/ morphological index determination, 236-242 potential control of stoichiometry, 234-235 reactions, 231-232 reasons for interest, 232 role of electrochemical parameters, 234-242 schematic representation of conventional electrocrystallization cell, 231,233/ Electrodeposition of nanoscale artificially layered ceramics, 244-253 composition and cubic lattice parameters vs. applied current density, 248f double galvanostatic pulse for electrodeposition, 246,247/ epitaxial growth vs. composition, 249,251-252/253 experimental procedure, 246 quantum confinement vs. optical and electrical properties, 253 SEM offilms,248,25Qf XRD pattern for superlattices, 248-250 Electron donors and acceptors, synthesis and deposition as components of zirconium diphosphonate multilayer films, 24-31 Electron-transport chains in zeolites, self-assembling, 333-345 Electrooptical liquid-crystalline sol-gel glasses, preparation, 396 Empty cage structure, 296 Encapsulation of organic molecules and enzymes in sol-gel glasses, 384-403 Encapsulation strategies for zeolite inclusion chemistry adsorption and diffusion from gas or liquid phase, 278 incorporation during hydrothermal synthesis, 278

Encapsulation strategies for zeolite inclusion chemistry—Continued ion exchange, 278 palladium ensembles in zeolites, 279,28Qf,281,282/ polyacrylonitrile chains in zeolite channels, 287,288/289 quantum-size cadmium selenide clusters in zeolite Y , 281,283,284/ reactivity of trimethyltin manganesepentacarbonyl in zeolite cavities, 283,285,286/287 Enzymes, encapsulation in sol-gel glasses, 384-403 Exfoliation, low-dimensional solids, 106,108,109-1 lQf External oxidants, preparation of polymers in host structures, 195

Fluorescent dyes in sol-gel glasses, examples, 397

γ form of zirconium phosphate, 178 Gold, adsorption of self-assembled monolayers, 11,12/13 Grazing angle FTIR method, use for studies of Langmuir-Blodgett films of Ru(II) complexes, 47-48 Guests, description, 315

Hard tissue, formation, 61-62 Heterogeneous nucleation, 62-63,65/ High-current techniques using STM for surface modification, 76-79 High-voltage techniques, See High-current techniques using STM for surface modification Highly ordered pyrolytic graphite, modification using high-current STM techniques, 77



432


Hofmann-type inclusion compounds determination of polymer location by EPR spectroscopy, 210,21 1/ FUR spectra, 207,208/ oxidation of aniline vs. that of pyrrole, 207 selected area electron diffraction patterns, 207,209/ structure, 204,207 Hole burning, use of sol-gel glasses, 396 Honeycomb framework, hexagonal channels, 261,263/ Host-guest inclusion compounds, relationship of structure and bonding properties to spatial and topological host-guest compatibility, 314 Hydrogen-bonded networks crystalline substructures, 16-17,18/ examples, 18,19-21/ hydrogen bond-crystallization relationship, 16,17/

Inorganically pillared clays, use as petroleum cracking catalysts, 128 Insulators, synthesis and deposition as components of zirconium diphosphonate multilayer films, 24-31 Intercalated polymers in structurally defined hosts, 194 Intercalation aniline in layered protonic conductors, 220-229 layered inorganic solids, applications of products, 166 organic guest molecules into inorganic hosts, reaction types, 167 Iron oxychloride as precursor to lamellar iron phosphonates, 114-126 crystallographic parameters of iron phosphonates, 118/ kinetic relations between iron phosphonates, 116,117/ magnetic susceptibility of F e ^ H ^ ^ · HjO, 121,124/ Mossbauer and IR spectra of α, β, and γ phases of H F e i Ç f t P O ^ · IÔ, 121,122/ phosphonic acid-FeOQ molar ratio vs. kinetics, 116 possible structural change upon transition from HFe(C H^0 K) to

In situ intercalative polymerization, insertion of polymer chains into host structures, 194-195 Inclusion polymerization of conducting polymers, design, 4 Infinite two- and three-dimensional frameworks, novel materials, 256-272 cavities and channels, 257 diamond-related frameworks, 258,259-26Qf,261 future research, 269,273 honeycomb net, 261,262-263/ interpénétration, 257 interpénétration of square grid sheets to form novel three-dimensional network, 261,264-265/266 preparation of unusual materials, 256-257 PtS-related frameworks, 269,270-272/" rutile-relatedframeworks,266,267/ three-dimensional net with four connected porphyrin building blocks, 266,268/269 Inorganic glasses, trapping of organic molecules, 385-386 Inorganic hosts, crystalline as media for conductive polymer synthesis, 194-218 description, 315

6

3

A

HFe(RP03> · *H 0,118.12QT 2

2

solvent vs. kinetics, 115; structure of Fe(C H P0 ) · H p , 121,123/ structure of FeiHP0 C H C0 H) ,121,125/ structure of HFe(C 2H P0 2H) , 116,118,119/ structure of HFeiRPO^ · xHfi, 118,121 synthesis, 115 Iron particle catalyst, trapping in sol-gel glasses, 390 Iron phosphonates, lamellar, iron oxychloride as precursor, 114-126 Iron phthalocyanines, NaX zeolite synthesis, 349-353 2

5

3

6

3

2

5

4

2

3

2

4

L Lamellar iron phosphonates, iron oxychloride as precursor, 114-125 Langmuir-Blodgett films of Ru(H) complexes spherical model for packing of stearic acid-Ru complex mixtures, 53,58/59


433


INDEX Uingmuir-Blodgett films of Ru(H) complexes—Continued STM image of stearic acid coated Ag substrate, 53,56/ STM image of stearic acid-Ru complex coated Ag substrate, 53,56-57/ top view of stearic acid-metal complex cluster, 53,58/ Langmuir-Blodgett films of transitionmetal complexes, 46-60 adsorption spectrum of stearic acid-Ru complex film, 49,52^53 application to Ru(II) complexes, 47 coating vs. indium tin oxide, 46 emission spectrum of stearic acid-Ru complex film, 4 9 , 5 ^ 3 experimental materials, 49 film preparation procedure, 48 grazing angle FTIR spectrum for stearic acid-Ru complex film, 53,54/ KBr pellet spectrum of metal complex, 53,55/ KBr pellet spectrum of stearic acid, 5334/ measurement procedure, 49 preparation using mixed layer strategy, 47 pressure-area isotherm for pure stearic acid,49,5(y pressure-area isotherm for stearic complex acid-Ru films, 49,51/ problems with long-chain alkyl, ester, and acid functions, 46 STM image of Ag substrate, 53,55/ Laser dyes embodied in optically clear supported thin-film glasses, 405-423 Layered double hydroxides, pillaring, 138-139 Layered materials, pillared, 128-143 Layered metal phosphonate(s), structure, 166-167 Layered metal phosphonate thin films, template approach, 3 Layered phosphates, pillaring, 139-140 Layered protonic conductors, intercalation and polymerization of aniline, 220-229 Layered structures, 3-4 Layered transition-metal dichalcogenides, solid-state metathesis routes, 369-382 Layered zirconium phosphates, polyether and polyimine derivatives, 178-192

Lead(IV) oxide electrodeposition, 246-253 semiconductor properties, 246 transmission optical spectra of thick films, 246,247/ Light-absorbing materials from sol-gel glasses electrooptical liquid-crystalline sol-gel glasses, 396 hole burning and nonlinear optics glasses, 396 photochromic glasses, 394-395 Light-emitting materials from sol-gel glasses, fluorescent and dye laser materials, 396-398 Light-induced electron transfer, photodiodes, 336-338,34(y Low-dimensional materials, approaches to macromolecular constructions, 33 Low-dimensional molecular solids, electrocrystallization, 231-243 Low-dimensional Ru materials, 33-45 mixed inorganic-organic polymers, 38,41-44 self-assembled multilayers, 34-40,42 Low-dimensional solids, 88-112 acid-base soft chemistry, 106,107/ chemical reactivity, 88 compositional variations, 95,96/ counterfoils vs. stability, 101-102,103/ crystal chemistry, 89-90,91/92 dimensionality, 92,94/95 exfoliation reactions, 106,108,109-1 lOf increasing tonicity of bonds, 95,98,99-10Qf,101 physical properties, 88 redox soft chemistry preparations, 102,104,105/ M Macromolecular assemblies, design of solid-state structures, 10 Mechanical techniques using STM for surface modification examples, 80 line scan of square holes etched into SnSe surface, 81,82/ mechanism of layer-by-layer etching process, 80 triangular morphology of etching, 81,83/ 2



434


Melamine, structure, 16 Melamine-barbituric acid crystals crystalline substructures, 16-17,18/ examples, 18,19-21/ Melamine-isocyanuric acid complex, hydrogen-bonded sheet network, 16,17/ Melamine-isocyanuric acid reaction, 5 Metal phosphonates, applications, 114 Metallophthalocyanines structure, 347-348/ synthesis of NaX zeolites, 349-353 Metastable amorphous alloys, synthetic techniques, 356 Metathesis, solid-state routes to layered transition-metal dichalcogenides and refractory materials, 369-382 Microporous inorganic solids, advantages as organizing media for molecular electron-transport assemblies, 333 Mixed inorganic-organic polymers of ruthenium, See Ruthenium mixed inorganic-organic polymers Modulation wavelength, comparison for ceramic superiattices, 249; Molecular arrays, ordered, designing in two and three dimensions, 10-22 Molecular bilayer rectifiers and photodiodes, self-assembling electrontransport chains in zeolites, 333-345 Molecular diodes and photodiodes, 5 Molecular interactions, complexity of naturally occurring, 1-2 Molecular recognition, high level of control over molecular interactions, 1 Molecular rectifiers, analogy with p-n junction device, 333-334,335/ Molecular self-assemblies of ruthenium, See Ruthenium molecular self-assemblies Molecular solids, low-dimensional, electrocrystallization, 231-243 Molybdenum disulfide applications, 370-371 experimental hazards, 371,373 synthesis via solid-state metathesis, 371 XRD patterns, 371,372/ Mordenite, structure, 276;,277/ Morphological index, determination, 236-242 MoS , redox soft chemistry preparation, 104,105/ Multilayered repeating structures, 4

Multiple quantum wells, 244-246

2

Ν Nanomodulated superiattices, electrodeposition, 246 Nanoscale artificially layered ceramics, electrodeposition, 244-253 Nanoscale surface-modification techniques using STM, 76-85 chemical methods, 77,80 controlled manipulation of individual atoms, 84 high-current techniques, 76-77,78-79; mechanical techniques, 80-81,82-83/ Nanostructure photonic and electronic components, progress toward goal, 294 NaX zeolite synthesis with metallophthalocyanines additives vs. crystallization, 352-353/ electronic spectra, 350,351/ experimental procedure, 349 loadings of metal complex, 349,350; metallophthalocyanine complex vs. reactivity, 350-352 Nb Se Br , mixed-chain structure, 102 Niobium diselenide dimensionality, 92,94/95 structure, 92,93/ Niobium triselenide dimensionality, 92,94/95 increasing tonicity of bonds, 95,98,99-100,101/ structure, 92,93/ Non-cross-linked polyether derivatives of α-zirconium phosphate basal spacing, 181,183/ dispersion, 184 IR spectra, 179,18Qf polyethylene glycol esters, 181,182;,184/ schematic representation of layers in α-zirconium phosphate, 179,180/" synthesis of polyether phosphates, 179,181 synthesis of polyethylene oxide phosphates, 170 Nonlinear optics, use of sol-gel glasses, 396 Nucleation proteins, function, 63-64 Nucleophilic displacement reactions, catalysis using organoclay assemblies, 151,152;,153 3

10

2


435

INDEX


Ο Optically clear supported thin-film glass synthesis using sol-gel process, 405-423 absorbance and fluorescence characteristics of laser dyes embodied in sol-gel glasses, 420,421/422* blocking of one Si substituent, 411-412 contraction of sol-gel, 408,409* curing and final stabilization of supported glass, 416-417 distillation out of methanol, 415,416* experimental setup, 406-407 experiments and observations under acid catalysis, 412*,413 fast sol-gel process under basic catalysis, 419-420 fast sol-gel reactions, 417*,418/ film thickness determination procedure, 407 fracture of sol-gel, 409-410 future research, 423 gel reformation and relaxation processes, 41Qf guest molecules embodied in fast sol-gel matrices, 418-419 homogeneity principle, 413/,415 liquid-gel phase separation, 407-408 liquid-liquid phase separation, 407 molar ratio limiting value, 415 multilayered glasses and waveguides, 419 phase separation in cast films, 412 preparation of support glasses, 406 principles, 422-423 procedure for monitoring progress of polymerization and casting, 407 Si atoms bound to polymer by two substituents, 410,411/ Ordered molecular arrays, designing in two and three dimensions, 10-22 Organic hosts, description, 315 Organic-inorganic layered phosphonates, examples, 114 Organic molecular systems, control of molecular interactions, 1 Organic molecules, trapping in inorganic glasses, 385-386 Organic thin films, production approaches for architectural control, 24 Organoclay, description, 145

Organoclay assemblies, 145-153 advantages for use as triphasé catalysts, 150-151 basal spacings, 148 catalysis of nucleophilic displacement reactions, 151,152*,153 experimental materials, 146 idealized composition, 148 inertness toward Na and K salts of nucleophilic reagents, 150 organohectorite preparation procedure, 146 phase-transfer catalysis procedure, 146,148 pseudo-first-order rate constants for cyanation of /i-pentyl bromide, 150,151* stabilization of oil-water-type emulsions, 150 structures, 145-146,147/ XRD pattern for oriented film sample, 148,149/ Orthogonal self-assembly, description, 3 Oxides, pillaring, 140 +

+

Ρ p-n junction device, analogy with molecular rectifier, 333-334,335/ Palladium ensembles in zeolites geometric arrangements, 281,282/ reaction conditions vs. particle size, 279 treatments vs. encapsulation, 279,28Qf Periodic packaging, three-dimensional, 294-312 Perovskite layered compounds, 140,141/ Pharmacosiderite, three-dimensional periodic packaging, 309 Phosphorescent sol-gel glasses, 398 Photochromic compounds, use as probe molecules for mechanistic studies of sol-gel-xerogel transitions and cage properties, 400 Photochromic glasses, photochromic behavior, 394-395 Photodiodes, light-induced electron transfer, 336-338,34Qf Photoreactive sol-gel glasses back-reaction retardation, 388 evidence, 386-387 mechanism, 386-387 photochemical light-energy conversion, 388-389


436


Physicochemical property optimization of materials, strategies, 220 Pillared layered materials, 128-143 cation effect, 136 clays, 130,132-138 formation, 130,132/" history, 128 hydrolysis of A l vs. pH, 130,132/ interiayer spacing of smectite, 130 layered double hydroxides, 138-139 layered phosphates, 139-140 model of cross-linking by inversion of tetrahedral unit, 136,137/ molecular sieve properties, 133* NMR spectra, 134,135/136 oxides, 140 perovskite layered compounds, 140,141/ pfflaringbyZKIV), 138 pore size distribution, 133* sorption, 134* surface area distribution, 130,133* Polyacrylonitrile chains in zeolite channels, polymerization, 287,288/ Polyamine copper(II) complexes, trapping in sol-gel glasses, 391 Polyaniline, insertion in FeOQ, 196-203 Polyether(s), function as ionic conductors, 178 Polyether derivatives of α-zirconium phosphate diphosphate esters, 183,185* non-cross-linked derivatives, 179 Polyether phosphates, synthesis, 179,181 Polyethylene, use in biomimetic thin-film synthesis, 64-73 Polyethylene glycol esters of zirconium phosphate characterization, 181,182* dispersion, 184 synthesis, 181 thermogravimetric analysis, 181,184/ Polyethylene oxide diphosphate ester, synthesis, 191 Polyethylene oxide monophosphate, synthesis, 191 Polyethylene oxide phosphates, synthesis, 179 Polyfuran, insertion in FeOQ, 203 Polyimine derivatives of layered zirconium phosphates, 178-192


13

Polymerization, aniline in layered protonic conductors, 220-229 Polymers conductive, crystalline inorganic hosts as media for synthesis, 195-217 zeolite inclusion chemistry, 274-292 Porous amorphous inorganic materials, structural control, 6 Porphyrin, thermal analysis, 155-164 Porphyrin building blocks, threedimensional net, 266,268/269 Porphyrin-clay complexes, thermal analysis, 155-164 Potassium tetratitanate, 106,107/ Precursor synthetic methods, 369-370 Properties, novel low-dimensional Ru materials, 33-45 Protonic conductors, layered, intercalation and polymerization of aniline, 220-229 PtS-related frameworks structure, 269,270-271/ tetragonal unit cell, 269,272/ Pyrene, use as probe molecule for mechanistic studies of sol-gel-xerogel transitions and cage properties, 398-399

Q Quantum dots, zeolite inclusion chemistry, 274-292 Quantum-size cadmium selenide clusters in zeolite Y geometric arrangements, 283,284/ reaction conditions vs. encapsulation, 281,283 synthesis, 281 R Refractory materials, solid-state metathesisroutes,369-382 Rhodamines, use as probe molecules for mechanistic studies of sol-gel-xerogel transitions and cage properties, 400 Ruthenium(II) complexes, LangmuirBlodgett films, 46-59 Ruthenium(H) diimine complexes, spatial extent of lowest unoccupied molecular orbital, 47,5Qf


437


INDEX Ruthenium mixed inorganic-organic polymers, 33-45 advantages, 38,41 characterization, 41,43f IR spectral data, 41,43r magnetic measurements, 41,43i,44 synthetic procedure, 41,42/ Ruthenium molecular self-assemblies advantage, 34 Auger electron spectrum, 38,42/ ellipsometric measurements, 38,39/ experimental procedure, 34 formation of molecular self-assemblies, 34 functionalization of quartz substrate, 34 low-temperature Ru mirror formation procedure, 34-35 molecular self-assemblies, 34 STM images of Ru mirrors, 38,4Qf surface analytical procedure, 35 surface characterization, 35 synthesis of hexaaquaruthenium(II) complex, 34 synthetic approach, 35-36 X-ray photoelectron spectrum of C(ls) and Ru(3d) region, 35,37/ Rutile-related frameworks, structure of Zn[C(CN) ] ,266,267/ 3

2

Scanning electrochemical microscope (SEM), comparison to STM, 80 Scanning tunneling microscope (STM) for nanosecond surface-modification techniques, 76-84 speculative applications, 76 use for studies of Langmuir-Blodgett films of Ru(II) complexes, 48 use for surface modification on extremely fine scale, 76 Self-assembled monolayers adsorption onto copper, 14-15 adsorption onto gold, 11,12/13 adsorption onto silver, 13/14,15/ formation, 10-11 incorporation of tail groups, 14-15/ model for protein adsorption, X-rayinduced damage, and electron transfer, 13 polarized IR external reflection spectroscopy, 11,13-14

Self-assembled monolayers—Continued schematic representation of lattices, 11,12/ sensitivity to degree of oxidation of silver, 14 sensitivity to preparation conditions, 14 structures, 11,13,14-15 use in biomimetic thin-film synthesis, 64-73 wetting properties, 11-12 Self-assembled multilayers, lowdimensional Ru materials, 34-42 Self-assembling electron-transport chains in zeolites, 333-345 back-electron-transfer rate, 339,34(^,341 conformational flexibility vs. electrontransfer rates, 343,344/ covalently linked donor-acceptor molecules, 338-344 excitation vs. electron-transfer kinetics, 341,342/343 light-induced electron transfer, 336-338,34Qf Sheet packing, melamine-barbital complexes, 19-21 Ship-in-a-bottle complexes, preparation methods, 347-348 Silicalite, structure, 276f,277/ Silicon nitride, synthesis using silicon tetrachloride and ammonia, 370 Silver, adsorption of self-assembled monolayers, 13/14,15/ Si0 -supported catalysts, trapping in sol-gel glasses, 390-391 Smectite clays description, 129 house-of-cards structure, 130,131/ idealized structural formulas, 129f ion-exchange behavior, 129-130 oxygen positions defining micalike layer lattice structure, 145,147/ positive charge deficiency, 129 properties, 129 schematic representation, 129,131/ structural assemblies, 145-146,147/ Sodalite, applications, 5 Sodalite as model for three-dimensional periodic packaging, 294-312 atom cluster combinations, 307,3lOr empty cage structures, 296 examples of number of atoms in single cage, 296,298* 2


438


Sodalite as model for three-dimensional periodic packaging—Continued five-atom M X cage cluster, 296,298/ formal charge vs. framework composition, 296,299,300* framework atom substitution vs. inter-intracluster geometry, 301,304/305 limitations, 308 M X cubane-like cluster in structure cage, 296,297/ optical properties vs. charge, 299,301,302/ optical spectra for N a ^ color centers, 299,30Qf precision of cluster and packaging structural property determination, 305 sixty-atom truncated octahedron of structure, 295-296,297/ theoretical vs. experimental results for optical properties vs. charge, 301,303/ use of cage packaging for cluster and intercluster geometry control, 305,306/307 Soft chemistry approach to control of intermediates in solid-state syntheses, 356 components, 88 preparation of low-dimensional solids, 88-110 strategies, importance for lowdimensional structural design, 4 Sol-gel glasses copolymerization, 401 optical and spectroscopic applications, 394-398 Sol-gel process, 384-403 ability to trap organic molecules in inorganic glasses, 385-386 basic concept, 384 bioactive glasses, 391-394 chemically reactive organically doped sol-gel glasses, 386-391 preparation and properties of glasses, 385 preparation of optically clear supported thin-film glasses embodying laser dyes, 405-423 reviews, 405 synthesis of optically clear supported thin-film glasses, 406-423 trapping of catalytic metal and oxide particles, 390-391

Sol-gel reviews, precursors, 405 Sol-gel-xerogel mechanistic studies aromatic polycyclic molecules as probe molecules, 398 photochromic compounds as probe molecules, 400-401 pyrene and derivatives as probe molecules, 398-399 rhodamines as probe molecules, 400 Solid(s), low-dimensional, 88-112 Solid-solid interface reactions, working model for course, 357,358/ Solid-state materials, effect of control of reaction intermediates on tailoring structure, 355-356 Solid-state metathesis routes to layered transition-metal dichalcogenides and refractory materials, 369-382 advantages, 370 application to solid solutions, 382 effective control of temperature, 377-382 experimental procedure, 370-371,372/373 heat sink vs. temperature and crystaUinity, 377,379,38(^,382 initiation, 377 molybdenum disulfide, 370-371,372/373 NaCl vs. particle size, 379*,381/ precursor selection, 375,376*378/ SEM of reaction products before and after washing, 377,378/ thermodynamics, 373,374/ Solid-state structures design using hydrogen-bonded networks, 16-21 design using self-assembled monolayers, 10-16 Sorption of electrolytes by zirconium polyether compounds interaction with alkali thiocyanates, 186,187* measurement of ionic conductivity, 186,187/188,189/ uptake of CuC^, 183,185*,186 Spiropyranes, photochromic behavior, 395 Square-grid two-dimensional sheets, interpénétration to form three-dimensional network, 261,264-265/266

4


4

4


439


INDEX Superlattice band structures of doping and compositional superiattices, 244,245/ definition, 244 design, 4 idealized structure, 244,245/ Superlattice reactants, synthesis of metastable amorphous intermediates and crystalline products, 355-367 Supported thin-film glasses, optically clear, synthesis using sol-gel process, 405-423 Supramolecular assemblies, importance of control, 2 Surface-modification techniques, nanoscale, See Nanoscale surfacemodification techniques using STM Synthesis asymmetrically layered zirconium phosphonates, 166-176 biomimetic thin films, 61-75 conductive polymers, crystalline inorganic hosts as media, 194-218 electron donors, acceptors, and insulators as components of zirconium diphosphonate multilayer films, 24-32 known materials, demand for new approaches, 6 NaX zeolites with metallophthalocyanines, 347-353 novel low-dimensional Ru materials, 33-45 via superlattice reactants, 355-367 Synthetic organoclay complexes, reasons for interest in thermal characteristics, 155-156

Τ Template(s), applications, 2 Template concept, description, 2 Tetrachalcogenides, effect of ionicity of bonds, 98,l(Xy;i01 Tetraethoxysilane, use as sol-gel precursor, 406 Tetra(isopentyl)ammonium fluoride, three-dimensional periodic packaging, 209 Thallium(III) oxide electrodeposition, 246-253 transmission optical spectra of thick films, 246,247/

Thermal analysis of porphyrm-clay complexes, 155-164 calculation of decomposition products from porphyrins, 162,164* characterization of porphyrin-clay complexes, 156,157* characterization procedure, 156-157 pyrolysis-GC-MS of complexes, 158,161,162* pyrolysis-GC-MS of porphyrins, 158,161,162*,163/ structures of porphyrins, 156 synthetic procedure, 156 thermal analysis of clays, 157-158,159/161* thermal analysis of complexes, 157-158,16Qf,161* thermal analysis of porphyrins, 157-158,159/161* Thinfilm(s),examples, 2-3 Thin-film ceramic materials, importance of ability to control orientation, 62 Thin-film glasses, optically clear, synthesis using sol-gel process, 405-423 Thin-film synthesis, biomimetic, 61-75 Three-dimensional frameworks, 4-5 Three-dimensional materials, synthesis via precursor methods, 369 Three-dimensional net with porphyrin building blocks, 266,268/269 Three-dimensional periodic packaging, 294-312 additional property requirements, 308 cocoxenite, 309 l,4-diazabicyclo[2.2.2]octane, 309 pharmacosiderite, 309 property requirements, 295 sodalite as model, 295-308 tetra(isopentyl)ammonium fluoride, 309 zeolite X, 309 Topotactic kinetics in zeolite nanoreaction chambers, 314-331 activation parameters for dissociative reactions of Mo( CO) ,322*,323/ choosing archetypal intrazeolite reaction, 316-317 classes of reactivity behavior for dissociative substitutions, 322,323/324 CO pressure effects on rates, 326-330 CO substitution kinetics, 320-324 description of chambers, 315-316 12

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Topotactic kinetics in zeolite nanoreaction chambers—Continued experimental design, 317-319 loading-dependent adsorption effects, 319-320,321/ mechanism, 324-325 mid-IR spectral traces of kinetics run, 320,321/322 Mo( CO) loading effects without added CO, 325-326 PMe loading effects without added CO, 325 summary, 329,331 Transistors, use of thin films, 3 Transition-metal chalcogemdes, band scheme models, 90,91/92 Transition-metal complexes, Langmuir-Blodgett films, 46-59 Transition-metal dichalcogenides, synthesis using lithium sulfide and titanium tetrachloride, 370 Trimethyltin manganesepentacarbonyl reactivity in zeolite cavities, 285-287 Triphasé catalytic system description, 148,150 limitations, 150 organoclay assemblies, 150-153 Two-dimensional assemblies, 2-3 Two-dimensional materials, synthesis via precursor methods, 369

Zeolite(s)—Continued applications, 4-5 description, 275 formula, 275 kinetics, 5 knowledge about chemical reactivities of imbibed guests, 315 molecular partitioning, 334,335/336 NaX, synthesis, 347-353 self-assembling electron-transport chains, 333-345 structural integrity upon encapsulation or intercalation, 275 structural types, 275,276f,277/ structural units, 275 synthesis, 277 Zeolite A, structure, 275,276f,277/ Zeolite cavities, reactivity of trimethyltin manganesepentacarbonyl, 283,285,286/287 Zeolite-encapsulated metal chelate complexes, application in catalysis, 347 Zeolite inclusion chemistry, encapsulation strategies, 278-289 Zeolite nanoreaction chambers, topotactic kinetics, 314-331 Zeolite X, structure, 275,276f,277/ Zeolite Y, structure, 275 Zeozymes, definition, 347 Zirconium diphosphonate multilayer films, 24-32 absorbance vs. layer number, 28,31/ characterization, 28,30-31/ deposition procedure, 26,28 electrical measurements, 28 electrochemical properties, 26 ellipsometric thickness vs. layer number, 28,3Qf layer arrangements, 28,29/ schematic representation, 24,25/26 syntheses of organodiphosphonates, 26,27/ Zirconium hydrogen phosphates intercalation of aniline, 223-224 structure, 221 α-Zirconium phosphate, polyether derivatives, 179-185 Zirconium phosphonates, asymmetrically layered, See Asymmetrically layered zirconium phosphonates

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U Ultrathin-film multilayer composites, advantages for preparation of amorphous solids, 356,357,358/ W Well-ordered organic macromolecules inside inorganic host structures external oxidant method, 194 in situ intercalative polymerization method, 194-195

Ζ Zeolite(s) acidity, 278 adsorption, 277-278



INDEX Zirconium polyether compounds experimental procedure, 191-193 sorption of electrolytes, 184-189 Zirconium polyether oxide phosphate reaction with Cu(II), 192 reaction with NaSCN and LiSCN, 192 synthesis, 191-192 Zirconium polyethylene oxide phosphates, basal spacing, 181,183/ Zirconium polyimine phosphonates characterization, 188,189; degree of swelling vs. protonation, 188,19Qf,191 experimental procedure, 191-193 synthesis, 188

Zr-COOH-H IR spectroscopy of products from reaction with SOC^, 172,173-174 synthesis, 171 thermogravimetric analysis, 171 XRD pattern, 171-172 Zr-COOH-OH C, H, and Ν analysis, 171 IR spectra of products from reaction of SOO,, 173/174 spectroscopic data, 171 synthesis, 170 thermogravimetric analysis, 171 XRD patterns, 170-171

Production: Betsy Kulamer Indexing: Deborah H. Steiner Acquisition: Anne Wilson Printed and bound by Maple Press, York, PA


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