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Utilizing Metallosupramolecular Polymers As Smart UTILIZING METALLOSUPRAMOLECULAR POLYMERS AS SMART MATERIALS by JUSTIN R. KUMPFER Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Dissertation Adviser: Dr. Stuart J. Rowan Department of Macromolecular Science and Engineering CASE WESTERN RESERVE UNIVERSITY May, 2012 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of Justin Richard Kumpfer ____________________________________________________________ Doctor of Philosophy candidate for the_______________________________________degree.* Dr. Stuart Rowan (signed)_____________________________________________________ Dr. João Maia _____________________________________________________ Dr. Mohan Sankaran _____________________________________________________ Dr. David Schiraldi _____________________________________________________ March 20th, 2012 (date of defense)_____________________________ *We also certify that written approval has been obtained for any proprietary material contained therein. ii Table of Contents List of Figures vii Acknowledgments xv Abstract xvi Chapter 1: Introduction 1 1.1 Metal-Ligand Interactions 2 1.2 Metallosupramolecular Polymers 7 1.2.1 Main-Chain Metallosupramolecular Polymers 11 1.2.2 Side-Chain Metallosupramolecular Polymers 23 1.3 Thesis Scope 26 1.4 References 28 Chapter 2: Stimuli-Responsive Europium-Containing Metallosupramolecular Polymers 32 2.1 Introduction 33 2.2 Results and Discussion 37 2.2.1 Optical Properties of the Metallosupramolecular Polymer Films 40 2.2.2 Thermomechaincal Properties 44 2.2.3 Stimuli-Responsive Behavior 48 2.3 Conclusions 53 2.4 Experimental Methods 53 2.5 Acknowledgments 59 iii 2.6 References 60 Chapter 3: Influence of Metal-Ion and Polymer Core on the Melt Rheology of Metallosupramolecular Films 63 3.1 Introduction 64 3.2 Results and Discussion 65 3.2.1 Influence of Eu3+ Content 67 3.2.2 Influence of the Core Polymer 76 3.2.3 Response at High Strain 83 3.3 Conclusions 87 3.4 Experimental Methods 88 3.5 Acknowledgments 90 3.6 References 91 Chapter 4: Thermo-, Photo-, and Chemo-Responsive Shape-Memory Properties from Photocrosslinked Metallosupramolecular Polymers 95 4.1 Introduction 96 4.2 Results and Discussion 101 4.2.1 Material Properties 101 4.2.2 Thermally-Induced Shape-Memory Properties 106 4.2.3 Light-Induced Shape-Memory Properties 108 4.2.4 Effect of Different Metals and Counterions on the Light-Induced Shape-Memory Behavior 115 iv 4.2.5 Localized Shape-Memory Response 119 4.2.6 Chemo-Responsive Shape-Memory Effect 121 4.3 Conclusions 123 4.4 Experimental Methods 123 4.5 Acknowledgments 129 4.6 References 130 Chapter 5: Vapochromic and Piezochromic Films From Platinum Complex Polymer Blends 135 5.1 Introduction 136 5.2 Results and Discussion 139 5.2.1 Spectroscopic Studies 142 5.2.2 Structural Properties 150 5.2.3 Mechanochromic behavior 153 5.3 Conclusions 157 5.4 Experimental Methods 158 5.5 Acknowledgments 163 5.6 References 163 Chapter 6: Fabrication of Platinum Nanoparticles Utilizing Metallosupramolecular Polymers as Templates 169 6.1 Introduction 171 6.2 Results and Discussion 173 v 6.2.1 Morphological Studies 175 6.2.2 Reduction of Metallosupramolecular Polymers using Extracted Discharge 182 6.2.3 Nanoparticle Growth and Assembly 187 6.3 Conclusions 191 6.4 Experimental Methods 191 6.5 Acknowledgments 195 6.6 References 195 Chapter 7: Self-Assembly of Metallosupramolecular Polymers in the Melt 197 7.1 Introduction 198 7.2 Results and Discussion 200 7.2.1 Polymer Synthesis and Characterization 200 7.2.2 Self-Assembly in the Melt 205 7.3 Conclusions 215 7.4 Experimental 215 7.5 Acknowledgments 221 7.6 References 221 Bibliography 225 vi LIST OF FIGURES Figure 1.1 Examples of different metal-ligand coordination geometries. 3 Figure 1.2 a) Schematic representation of the equilibrium thermodynamic and kinetic properties of a 2:1 complex and b) schematic of selective ligand exchange. 5 Figure 1.3 Schematic representation of a metal-ligand complex for chemical sensing applications. 6 Figure 1.4 Schematic overview of some of the potential properties of metallosupramolecular polymers. 7 Figure 1.5 Influence of stoichiometry in main-chain supramolecular polymers on degree of polymerization as a function of concentration. 10 Figure 1.6 Example of dynamic ligand exchange between nonemissive compounds 1.4 and 1.5 to yield a new emissive polymer. 13 Figure 1.7 Structure of 1.7 used to prepared water soluble metallosupramolecular polymers and schematic of assembly with b) Nd3+ and c) Nd3+:Zn2+ in a 3:1 ratio. 15 Figure 1.8 Schematic illustration of the fabrication of a conducting metallosupramolecular polymer/electrode device for a nitric oxide sensor by measuring the resistance. 18 Figure 1.9 a) Images of stimuli-responsive metallosupramolecular gels which respond to electrical oxidation and reduction and b) the material properties as a function of the order of metal addition. 19 Figure 1.10 a) Schematic representation of the mechanism of optical healing of a metallosupramolecular polymer and images of self-healing with UV irradiation by b) AFM and c) visible recovery. 22 Figure 1.11 Example of side-chain metallosupramolecular polymers with lanthanides which demonstrate irreversible and/or reversible thermo-responsive changes in emission. 25 Figure 2.1 Synthesis of macromonomer 2. 37 vii Figure 2.2 a) 1H NMR of macromonomer 2 and b) plot of molecular weight of 2 vs polymerization time. 39 Figure 2.3 UV-vis titration curves of 2 with a) Eu(ClO4)3 and c) Zn(ClO4)2 along with determination of the binding ratios for b) Eu(ClO4)3 and d) Zn(ClO4)2. e) Schematic representation of the self-assembly of 2 with Zn2+ and Eu3+. 41 Figure 2.4 Picture before and after stretching of a Zn2+:Eu3+ 70:30 film with 2. 42 Figure 2.5 a) Images of the fluorescence of a series of films with Zn2+:Eu3+ ratios ranging from 100:0 to 50:50, b) the corresponding PL spectra, and c) schematic of the antenna effect. 43 Figure 2.6 DMTA temperature sweeps of films with Zn2+:Eu3+ 100:0-50:50 ratios a) annealed and b) unannealed. 45 Figure 2.7 DMTA temperature sweeps of films with Zn2+:Eu3+ 80:5-80:20 ratios. 46 Figure 2.8 a) WAXS diffractograms of select films with Zn2+:Eu3+ ratios of 100:0, 90:10, 70:30, and 50:50 and b) a schematic of the change in ordering as the amount of Eu3+ is increased. 48 Figure 2.9 a) Pictures of the thermal stimuli-responsive sensing capability of a Zn2+:Eu3+ 70:30 film. Influence on the PL spectra with temperature focusing on the Eu3+ metal-based emission as b) temperature is increased and c) temperature is cycled between room temperature and 120 °C. 50 Figure 2.10 Pictures of a Zn2+:Eu3+ 70:30 film a) as cast, b) dipped in a 10 mM solution of triethyl phosphate in hexanes for 1 min., c) exposed to triethyl phosphate vapor for 24 hrs., and d) dipped directly into triethyl phosphate along with d) the corresponding change in the PL spectra. 52 Figure 2.11 13C NMR of 2. 56 Figure 2.12 MALDI-TOF of 2. 56 Figure 2.13 MALDI-TOF-TOF of 2. 57 Figure 2.14 PL spectra of 2 with Zn2+:Eu3+ 100:0-50:50 in solution. 58 Figure 2.15 TGA of films of 2 with Zn2+:Eu3+ 100:0-50:50. 58 viii Figure 3.1 Chemical structures of macromonomers 2 and 3. 66 Figure 3.2 Master curves of films prepared with 2 containing Zn2+:Eu3+ 100:0-50:50 ratios. 69 Figure 3.3 Time-temperature superposition curves of tan δ vs ω a) for films prepared with 2 and Zn2+:Eu3+ 100:0-50:50 with temperatures ranging from 30 °C to 110 °C and b) a Zn2+:Eu3+ 60:40 film with 2 from -30 °C to 70 °C. 71 Figure 3.4 Shift factors a) horizontal and b) vertical for films prepared with 2 with Zn2+:Eu3+ 100:0-50:50 ratios. 73 Figure 3.5 Time-temperature superposition plot of complex viscosity vs ω for films prepared with 2 with Zn2+:Eu3+ 100:0-50:50 ratios. 76 Figure 3.6 TEM micrographs of a) 100% Zn(NTf2)2 and b) 100% La(NTf2)3 films prepared with 3. 78 Figure 3.7 SAXS of a) films prepared with 2 with Zn2+:Eu3+ 100:0-50:50 ratios and b) comparison of Zn2+:Eu3+ 100:0 films prepared with 2 and 3. c) Schematic of ordered self-assembly of 2 and 3 upon addition of Zn2+ and/or Eu3+. 79 Figure 3.8 Master curves comparing film prepared with 2 vs 3 for Zn2+:Eu3+ ratios of a) 100:0, b) 50:50, and c) 0:100. 81 Figure 3.9 a) Horizontal and b) vertical shift factors of film prepared with 2 and Zn2+:Eu3+ 0:100 and prepared with 3 with Zn2+:Eu3+ 100:0, 50:50, and 0:100. 82 Figure 3.10 Strain sweeps of films prepared with 2 and Zn2+:Eu3+ ratios a) 100:0, b) 90:10, c) 80:20, d) 70:30, e) 60:40, and f) 50:50 along with images of the stress response both inside and outside the viscoelastic region. 84 Figure 4.1 a) Example of typical shape-memory polymer behavior and b) an example of a typical one-way shape-memory curve. 97 Figure 4.2 Schematic of the mechanism of light-induced shape-memory behavior for films prepared with 4. 100 Figure 4.3 a) Synthesis of macromonomer 4 and b) 1H NMR of macromonomer 4. 102 ix Figure 4.4 Schematic of photocrosslinking of films prepared with 4 and Eu3+ using a tetrathiol crosslinker. 103 Figure 4.5 Pictures of using photocrosslinking to prepare a 4.1∙Eu(NTf2)3 film with a permanent spiral shape.
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