CYANOMETALLATE COORDINATION POLYMER NANOSTRUCTURES AND THIN FILMS: SYNTHESIS AND APPLICATIONS By IAN AMMON RUMMEL A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2009 1 © 2009 Ian Ammon Rummel 2 To my wife Julia 3 ACKNOWLEDGMENTS I thank my wife Julia for keeping me sane throughout gradschool, my advisor Dr. Talham, Dr. Mark Meisel, Elisabeth Knowles, all current and past members of the Talham group, Dr. Nathan Heston, Dr. John Reynolds, and UF MAIC, and my parents. 4 TABLE OF CONTENTS page ACKNOWLEDGMENTS .................................................................................................. 4 LIST OF FIGURES ..........................................................................................................8 LIST OF ABBREVIATIONS ........................................................................................... 15 ABSTRACT ................................................................................................................... 16 CHAPTER 1 INTRODUCTION TO SUPRAMOLECULAR CHEMISTRY AND SYNTHESIS AT THE AIR/WATER INTERFACE .............................................................................. 18 Supramolecular Chemistry ...................................................................................... 18 Supramolecular Assembly with Langmuir Monolayers ........................................... 19 Use of Langmuir Monolayers as a Structure-Directing Element ............................. 22 Characterization of Langmuir Monolayers with Underlying Cyanometallate Coordination Networks ........................................................................................ 24 Brewster Angle Microscopy .............................................................................. 24 Attenuated total reflectance infrared spectroscopy ...........................................25 Scope of the Thesis ................................................................................................ 26 2 PRIMITIVE SQUARE NETWORKS AT THE AIR-WATER INTERFACE ................ 32 Introduction ............................................................................................................. 32 Experimental ........................................................................................................... 34 Synthesis ..........................................................................................................34 Pentacyanoferrate amphiphile synthesis ................................................... 34 N-methyl-4-(didodecylamino)pyridinium iodide .......................................... 34 4-(Didodecylamino)pyridine ....................................................................... 34 Bis(tetramethylammonium)pentacyano(4-(didodecylamino)-pyridine) ferrate(III) ................................................................................................ 35 Ru(II/III)tetracarboxylate chloride ............................................................... 36 1,4,8,11-tetraazacyclotetradecane nickel (II) perchlorate .......................... 36 1-octadecyl-1,3,6,10,13-pentaazacyclotetradecane nickel (II) chloride ...... 37 Materials ...........................................................................................................37 Instrumentation ................................................................................................. 37 Langmuir Monolayer Preparation ..................................................................... 38 Results ....................................................................................................................39 Synthesis ..........................................................................................................39 Bis(tetramethylammonium)pentacyano(4-(didodecylamino)-pyridine) ferrate(III) ................................................................................................ 39 Ru(II/III)tetracarboxylate chloride ............................................................... 39 1,4,8,11-tetraazacyclotetradecane nickel (II) perchlorate .......................... 39 1-octadecyl-1,3,6,10,13-pentaazacyclotetradecane nickel (II) chloride ...... 40 5 II Macrocyclic Ni Amphiphile with K4Fe(CN)6 Subphase ...................................... 40 Surface pressure vs. mean molecular area isotherms ................................ 40 BAM ............................................................................................................... 40 ATR FT-IR ..................................................................................................... 41 XPS ................................................................................................................ 41 AFM................................................................................................................ 41 Creep observations ....................................................................................... 41 Pentacyanoferrate Amphiphile with Macrocyclic Tetraaza Ni (II) Subphase ..... 42 Surface pressure vs. mean molecular area isotherms ................................ 42 BAM ............................................................................................................... 43 XPS ................................................................................................................ 43 Pentacyanoferrate Amphiphile with Ru (II/III) Tetracarboxylate Subphase ....... 43 Surface pressure vs. mean molecular area isotherms ................................ 43 BAM ............................................................................................................... 44 ATR FT-IR ..................................................................................................... 44 XPS ................................................................................................................ 44 Discussion ................................................................................................................... 45 II Macrocyclic Ni Amphiphile with K4Fe(CN)6 Subphase ...................................... 45 Pentacyanoferrate Amphiphile with Macrocyclic Tetraaza Ni (II) Subphase ..... 46 Pentacyanoferrate Amphiphile with Ru (II/III) Tetracarboxylate Subphase ....... 47 General Discussion .............................................................................................. 47 Conclusions and Future Work .................................................................................... 49 3 CYANOMETALLATE OLIGOMERS AS BUILDING UNITS IN SUPRAMOLECULAR BUILDING BLOCKS AT THE AIR/WATER INTERFACE .... 68 Introduction ................................................................................................................. 68 Experimental ............................................................................................................... 69 Synthesis .............................................................................................................. 69 Monolayer Preparation......................................................................................... 69 Results ........................................................................................................................ 69 Surface Pressure vs. Mean Molecular Area Isotherms ...................................... 69 BAM ...................................................................................................................... 70 ATR FT-IR ............................................................................................................ 70 XPS....................................................................................................................... 70 SQUID Magnetometry.......................................................................................... 71 Discussion ................................................................................................................... 71 Conclusions ................................................................................................................ 73 4 PRUSSIAN BLUE/TITANIUM DIOXIDE NANOCOMPOSITES ................................ 79 Introduction ................................................................................................................. 79 Experimental ............................................................................................................... 83 Synthesis .............................................................................................................. 83 Prussian blue nanoparticles .......................................................................... 83 NiIICrIII PBA nanoparticles ............................................................................. 83 TiO2-Coated Prussian Blue Particles .................................................................. 84 6 Thallium Staining for TEM Analysis .............................................................. 84 Photo-oxidative Experiments ............................................................................... 84 Visible Light-Induced Charge Transfer Evaluation ....................................... 85 Materials ........................................................................................................ 85 Instrumentation .............................................................................................. 85 Results .......................................................................................................................