1. CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor method Often a close relation structurally between precursor phase and product Topotactic transformations

2. CHIMIE DOUCE: SOFT CHEMISTRY Tournaux synthesis of a new form of TiO 2 Beyond Rutile, Anatase, Brookite and Glassy form!!! KNO 3 (T o C)  K 2 O (source) K 2 O + 4TiO 2 (rutile, 1000 o C)  K 2 Ti 4 O 9 K 2 Ti 4 O 9 + HNO 3 (RT)  H 2 Ti 4 O 9.H 2 O H 2 Ti 4 O 9.H 2 O (500 o C)  4TiO 2 (new slab structure) + 2H 2 O

3. KIRKENDALL EFFECT IN TOURNAUX SYNTHESIS OF SLAB FORM OF TiO 2 16K + - 4Ti 4+ + 36TiO 2  8K 2 Ti 4 O 9 4Ti 4+ - 16K + + 9K 2 O  K 2 Ti 4 O 9 Overall reaction stoichiometry 9K 2 O + 36TiO 2  9K 2 Ti 4 O 9 RHS/LHS = 8/1 Kirkendall Ratio

4. RUTILE CRYSTAL STRUCTURE z x y

5. SEEING THE 1-D CHANELS IN RUTILE

6. NEW METASTABLE POLYMORPH OF TiO 2 BASED ON K 2 Ti 4 O 9 SLAB STRUCTURE - (010) PROJECTION SHOWN K + at y = 3/4 K + at y = 1/4 Different to rutile, anatase or brookite forms of TiO 2 1/2 1 1 1 1 1/3 1/2 1/2 x2 1/3 x2 Topotactic loss of H 2 O from H 2 Ti 4 O 9 to give “Ti 4 O 8 ” (TiO 2 slabs) plus H 2 O, where two bridging oxygens in slab are protonated (TiOHTiOTiOH)

7. CHIMIE DOUCE: SOFT CHEMISTRY Figlarz synthesis of new WO 3 WO 3 (cubic form) + 2NaOH  Na 2 WO 4 + H 2 O Na 2 WO 4 + HCl (aq)  gel Gel (hydrothermal)  3WO 3.H 2 O 3WO 3.H 2 O (air, 420 o C)  WO 3 (hexagonal tunnel structural form of tungsten trioxide) More open tunnel form than cubic ReO 3 form of WO 3

8. Slightly tilted cubic polymorph of WO 3 with corner sharing Oh WO 6 building blocks, only protons and smaller alkali cations can be injected into cubic shaped voids in structure to form bronzes like Na x WO 3 and H x WO 3 1-D hexagonal tunnel polymorph of WO 3 with corner sharing Oh WO 6 building blocks, can inject larger alkali and alkaline earth cations into structure to form bronzes like Rb x WO 3 and Ba x WO 3 as well as H x WO 3 a 1D proton conductor having mobile protons diffusing from O site to site along channels

9. Hexagonal tunnels Injection of larger M + cations like K + and Ba 2+ than maximum of Li + and H + in c-WO 3 Apex sharing WO6 Oh building blocks Structure of h-WO 3 showing large 1-D tunnels

10. Functional device, LED, laser, sensor, biolabel High T solvent, ligand, protection, amphiphilic amines, carboxylic acids, phosphines, phosphine oxides, phosphonic acids Inorganic precursor, oxides, sulphides, metals, nucleation of nanocluster seed Growth and ligand capping of nanocluster core Ligand capping arrested growth of nanocluster core

11. Arrested nucleation and growth synthetic method for making semiconductor nanoclusters in a high-boiling solvent. Adding a non-solvent causes the larger nanocrystals to precipitate first, allowing size-selective precipitation and nanocluster scaling laws to be defined nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P

12. ARRESTED GROWTH OF MONODISPERSED NANOCLUSTERS Hydrophobic sheath of alkane chains of surfactant make the nanoclusters soluble in non-polar solvents - crucial for achieving purification and size selective crystallization of the nanoclusters. nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P Tributylphosphine selenide in a syringe is rapidly injected into a 300  C solution of dimethyl cadmium in trioctylphosphine oxide surfactant-ligand-solvent, known as TOPO.

13. SIZE SELECTIVE CRYSTALLIZATION OF LIGAND CAPPED NANOCLUSTERS Gradually add non-solvent acetone to a toluene solution of capped nanoclusters Causes larger crystals to precipitate then smaller and smaller crystals as the non-solvent concentration increases. Smaller ones more soluble because of easier solvation of less dense packed alkanethiolate chains.

14. SIZE SELECTIVE CRYSTALLIZATION OF LIGAND CAPPED NANOCLUSTERS When non-solvent added, nc-nc contacts become more favorable than nc-solvent interactions. Larger diameter capped nanoclusters interact via the chains of the alkanethiolate capping ligands more strongly than the smaller ones due to the smaller curvature of their surface and the resulting greater interaction area. As a result they are caused to flocculate that is aggregate and crystallize first.

15. SIZE SELECTIVE CRYSTALLIZATION OF LIGAND CAPPED NANOCLUSTERS Process repeated to obtain next lower size nanoclusters and procedure repeated to obtain monodispersed alkanethiolate capped gold nanoclusters. Further narrowing of nanocluster size distribution achieved by gel electrophoresis – an electric field driven size exclusion separation stationary phase.

16. Addition of reagent nucleation aggregation BASICS OF NANOCLUSTER NUCLEATION, GROWTH, CRYSTALLIZATION AND CAPPING STABILIZATION capping and stabilization nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P  G b >  G s supersaturation

17. CAPPED MONODISPERSED SEMICONDUCTOR NANOCLUSTERS nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P E g C = E g B + (h 2 /8R 2 )(1/m e * + 1/m h *) - 1.8e 2 /  R Coulomb interaction between e-h Quantum localization term

20. SIZE DEPENDENT OPTICAL ABSORPTION SPECTRA OF CAPPED CDSE NANOCLUSTERS, SYNTHESIS AND CHARACTERIZATION OF NEARLY MONODISPERSE CdE (E = S, Se, Te) SEMICONDUCTOR NANOCRYSTALLITES, MURRAY CB, NORRIS DJ, BAWENDI MG, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 115 (19): 8706-8715 SEP 22 1993)

21. SIZE AND COMPOSITION DEPENDENCE OF THE OPTICAL EMISSION SPECTRA OF CAPPED InAs (RED), InP (GREEN) AND CdSe (BLUE), BRUCHEZ, M.JR; MORONNE, M.; GIN, P.; WEISS, S.; ALIVISATOS, A.P. SEMICONDUCTOR NANOCRYSTALS AS FLUORESCENT BIOLOGICAL LABELS, SCIENCE 1998, 281, 2013

22. Nanocluster Synthetic Control – size, shape, composition, surface chemical and physical properties, separation, amorphous, crystalline Do it yourself quantum mechanics – synthetic design of optical, electrical, magnetic properties PXRD, MALDI-MS, TEM CHARACTERIZATION OF CLUSTER CORE, CLUSTER SEPARATION LIGAND SHEATH,

23. ARRESTED GROWTH OF MONODISPERSED NANOCLUSTERS CRYSTALS, FILMS AND LITHOGRAPHIC PATTERNS nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P

24. MONODISPERSED CAPPED CLUSTER SINGLE CRYSTALS methanol 2-propanol toluene Rogach AFM 2002

25. TRI-LAYER SOLVENT DIFFUSION CRYSTALLIZATION OF CAPPED NANOCLUSTER SINGLE CRYSTALS. MeOH TOP LAYER, TOLUENE BOTTOM LAYER, 2-PROPANOL MIDDLE BUFFER LAYER - OMITTING THE BUFFER LAYER CREATED ILL-DEFINED CRYSTALS, A NEW APPROACH TO CRYSTALLIZATION OF CdSe NANOPARTICLES INTO ORDERED THREE- DIMENSIONAL SUPERLATTICES, TALAPIN DV, SHEVCHENKO EV, KORNOWSKI A, GAPONIK N, HAASE M, ROGACH AL, WELLER H, ADVANCED MATERIALS, 13 (24): 1868, 2001

26. GOLD ATOMIC DISCRETE STATES GOLD CLUSTER DISCRETE MOLECULE STATES GOLD QUANTUM DOT CARRIER SPATIAL AND QUANTUM CONFINEMENT GOLD COLLOIDAL PARTICLE SURFACE PLASMON – 1850 MICHAEL FARADAY ROYAL INSTITUTION GB PIONEER OF NANO!!! BULK GOLD PLASMON

27. Relationship between alkanethiolate polymer, nanocluster and self-assembled monolayer

28. SELF-ASSEMBLING AUROTHIOL CLUSTERS HAuCl 4 (aq) + Oct 4 NBr (Et 2 O)  Oct 4 NAuCl 4 (Et 2 O) nOct 4 NAuCl 4 (Et 2 O) + mRSH (tol) + 3nNaBH 4  Au n (SR) m (tol) Diagnostic cluster size dependent optical plasmon resonance originating from dipole oscillations of conduction electrons spatially confined in nanocluster – wavelength plasmon depends on size, type of capping ligand and nature of the environment of nanocluster – also size dependent electrical conductivity – hopping from cluster to cluster - useful in nanoelectronic devices and nanooptical sensors – Faraday would be pleased!!!

29. SIZE SELECTIVE CRYSTALLIZATION OF SELF- ASSEMBLING AUROTHIOL CLUSTERS Au n (SR) m Gradually adding a non-solvent such as acetone to a toluene solution of capped gold nanoclusters first causes larger crystals to precipitate, then smaller and smaller crystals, as the non-solvent concentration increases. Smaller ones more soluble because of easier solvation of less dense packed alkanethiolate chains. When non-solvent added, nc-nc contacts become more favorable than nc-solvent interactions. Larger diameter capped gold nanoclusters interact via the chains of the alkanethiolate capping ligands more strongly than the smaller ones due to the smaller curvature of their surface and the resulting greater interaction area. As a result they are caused to flocculate that is aggregate and crystallize first. Process repeated to obtain next lower size nanoclusters and procedure repeated to obtain monodispersed alkanethiolate capped gold nanoclusters.

30. CAPPED METAL CLUSTER CRYSTAL CLUSTER SELF-ASSEMBLY DRIVEN BY HYDROPHOBIC INTERACTIONS BETWEEN ALKANE TAILS OF ALKANETHIOLATE CAPPING GROUPS ON GOLD NANOCRYSTALLITES

31. MIE THEORY SURFACE PLASMON RESONANCE MIE THEORY Extinction coefficient from Mie theory is the exact solution to Maxwell’s electromagnetic field equations for a plane wave interacting with a homogenous sphere of radius R with the same dielectric constant as bulk metal (scattering and absorption contributions).  m is the dielectric constant of the surrounding medium  1  i   is the complex dielectric constant of the particle. Resonance peak occurs whenever the condition  1 = -2  m is satisfied – sensitive to change in em of environment hence use as a surface plasmon sensor This is the SPR peak which accounts for the brilliant colors of various metal nanoparticles – form factors can be introduced to account for non-spherical shape – Gans modification of Mie theory.

32. Extinction spectra calculated using Mie theory for gold nanospheres with diameters varying from 5 nm to 100 nm.

33. Non-Spherical Shapes -Gans Modified Mie Theory

34. Au Nanorods – Shape Selective Additives Aspect Ratio Tunes Longitudinal NOT Transverse SPR Modes (a) L = 46 nm, w = 20 nm; (b) L = 61 nm, w = nm; (c) L = 73 nm, w = 22 nm; (d) L = 75 nm, w = 22 nm; (e) L = 89 nm, w = 22 nm; (f) L = 108 nm, w = 22 nm. The right panel shows a representative TEM image of the sample corresponding to spectrum-f. Calculated Gans Theory Gold Nanorod w = 20 nm

35. Gold Nanorods Aspect Ratio Tunes Longitudinal NOT Transverse SPR Modes NANOCHEMISTRY CURES CANCER CANCER CELL TARGETED GOLD NANOROD ATTACHMENT BURN AWAY THOSE NASTY CANCER CELLS BY NANORODS ABSORBING NIR PLASMON AND TRANSFERING HEAT TO CANCER CELL – PHOTOTHERMAL CANCER THERAPY

37. HIGH-DENSITY DATA STORAGE MATERIALS CAPPED FePt FERROMAGNETIC NANOCLUSTER SUPERLATTICE HIGH-DENSITY DATA STORAGE MATERIALS

38. NANOMAGNETIC SEPARATIONS OF BIOLOGICAL MOLECULES