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Mike Alvey PhD, Chemistry The University of Texas at Austin (2013) Department of Chemistry

Now Accepting Donations: Self-Assembly Through Aromatic Donor–Acceptor Interactions. Mike Alvey PhD, Chemistry The University of Texas at Austin (2013) Department of Chemistry Iverson Group September 19 , 2014. About Me. 2003-2007. 2013-Present. 2007-2013. Molecular Self-Assembly.

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Mike Alvey PhD, Chemistry The University of Texas at Austin (2013) Department of Chemistry

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  1. Now Accepting Donations: Self-Assembly Through Aromatic Donor–Acceptor Interactions Mike Alvey PhD, Chemistry The University of Texas at Austin (2013) Department of Chemistry Iverson Group September 19, 2014

  2. About Me 2003-2007 2013-Present 2007-2013

  3. Molecular Self-Assembly • Non-Covalent Interactions • Hydrogen Bonding • van der Waals Forces • Metal Coordination • Desolvation Bottom-Up Ordered Molecular Assembly

  4. Non-Covalent Interactions Hydrogen Bonding: Interaction Between Aromatics: Liu (2009) Nylon Kevlar Metal Coordination: Weder (2011) Nature,2011, 472, 334. J. Am. Chem. Soc. 2009, 132, 1110.

  5. DAN and NDI Crystal Structure Herringbone DAN NDI Crystal Structure Offset Face-to-Face Donor‒Acceptor (D‒A) Face-Centered Crystal Structure CT Absorbance Martinez, C. R.; Iverson, B. L. Chem. Sci. 2012, 3, 2191. Lokey, R. S.; Iverson, B. L. Nature ,1995, 375, 303.

  6. Aromatic Interactions DAN Electron-Rich NDI Electron-Deficient Face-Centered Herringbone Offset Face-to-Face Hunter, C.; Sanders, J. J Am. Chem. Soc. 1990, 112, 5525. Wheeler, S. ; Houk, K. J. Am. Chem. Soc. 2008, 130, 10854.

  7. Aromatic Interactions Hunter & Sanders Houk & Wheeler DAN Electron-Rich NDI Electron-Deficient Face-Centered Herringbone Offset Face-to-Face Hunter, C.; Sanders, J. J Am. Chem. Soc. 1990, 112, 5525. Wheeler, S. ; Houk, K. J. Am. Chem. Soc. 2008, 130, 10854.

  8. Aqueous DAN‒NDI Intramolecular D‒A NDI DAN Intermolecular D‒A Intermolecular D‒A Lokey, R. S.; Iverson, B. L. Nature ,1995, 375, 303. Gabriel, G. J.; Iverson, B. L. J. Am. Chem. Soc. 2002, 124, 15174 Reczek, J. J.; Iverson, B. L. Macromolecules2006, 39, 5601.

  9. Aqueous DAN‒NDI Intramolecular D‒A NDI DAN Intermolecular D‒A Intermolecular D‒A Lokey, R. S.; Iverson, B. L. Nature ,1995, 375, 303. Gabriel, G. J.; Iverson, B. L. J. Am. Chem. Soc. 2002, 124, 15174 Reczek, J. J.; Iverson, B. L. Macromolecules2006, 39, 5601.

  10. Aqueous DAN‒NDI Intramolecular D‒A NDI DAN Intermolecular D‒A Intermolecular D‒A Lokey, R. S.; Iverson, B. L. Nature ,1995, 375, 303. Gabriel, G. J.; Iverson, B. L. J. Am. Chem. Soc. 2002, 124, 15174 Reczek, J. J.; Iverson, B. L. Macromolecules2006, 39, 5601.

  11. Aqueous DAN‒NDI Association Constants (M-1) by NMR Titration DAN NDI From Study Cubberley, M.; Iverson, B. J. Am. Chem. Soc. 2001, 123, 7560.

  12. Aqueous DAN‒NDI Association Constants (M-1) by NMR Titration DAN NDI Electrostatic Motive From Study Cubberley, M.; Iverson, B. J. Am. Chem. Soc. 2001, 123, 7560.

  13. Aqueous DAN‒NDI Association Constants (M-1) by NMR Titration DAN NDI Electrostatic Motive From Study Desolvation as Driving Force Cubberley, M.; Iverson, B. J. Am. Chem. Soc. 2001, 123, 7560.

  14. States of Matter Dierking, I. Textures of Liquid Crystals, Revised Ed. Wiley-VCH: Weinheim, Germany, 2003; pp 1-3.

  15. DAN:NDI Liquid Crystals Heat Flow (W/g) Temperature (°C) DSC Cooling 2 °C/min: 123 °C 75 °C N12:D8 1 :4 POM (10X) N12 (160°C): R = N8 (181°C): R = N4 (226°C): R = 76 °C 140 °C 2 :4 N8:D8 D8 (76°C): R = 71 °C 182 °C N4:D8 3 :4 Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682. Reczek, J. J.; Villazor, K. R.; Lynch, V.; Swager, T. M.; Iverson, B. L. J. Am. Chem. Soc.2006, 128, 7995.

  16. Charge-Transfer Absorbance Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682. Reczek, J. J.; Villazor, K. R.; Lynch, V.; Swager, T. M.; Iverson, B. L. J. Am. Chem. Soc.2006, 128, 7995.

  17. Charge-Transfer Absorbance Isotropic Phase On Cooling Crystalline Phase Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682. Reczek, J. J.; Villazor, K. R.; Lynch, V.; Swager, T. M.; Iverson, B. L. J. Am. Chem. Soc.2006, 128, 7995.

  18. Scientific Question • Is the color change a result of steric interactions or are there • other factors that cause the components to separate? Original Hypothesis: Steric interactions result in separate domains of DAN and NDI upon cooling from the mesophase to the crystalline phase

  19. Component Library NDI = N DAN = D N4 = D8 = D3 = D9 = D4 = N8 = D10 = D5 = N12 = D3ʹ = D6 = N7ʹ = D5ʹR = D7 = N7ʹR = Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682. Pantos, D., et al. J. Org. Chem.2006, 71, 7063.

  20. Crystalline Mixture Colors Mixture Thermochromic Behavior Cooling Crystalline Phase Mesophase 20 Seconds (5X) D10N4 R P L Crystalline Phase Colors (5X) Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  21. Crystalline Mixture Colors Mixture Thermochromic Behavior Cooling Crystalline Phase Mesophase 20 Seconds (5X) D10N4 R P L Crystalline Phase Colors (5X) Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  22. Crystalline Mixture UV-Vis Spectra Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  23. Crystalline Mixture UV-Vis Spectra Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  24. Component Crystallization (A) (B) (D) (C) 5 °C/min cooling Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  25. Component Crystallization (A) (B) • Short Side Chains • High Crystallization Temperature • Strong Transition (D) 5 °C/min cooling Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  26. Component Crystallization (A) (B) • Long Side Chains • Low Crystallization Temperature • Broad Transition (D) (C) 5 °C/min cooling Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  27. Component Crystallization High Crystallization Temperature Components: 5 °C/min cooling Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  28. Component Crystallization High Crystallization Temperature Components: D3ʹ D3 5 °C/min cooling Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  29. Component Crystal Structure Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  30. Component Crystal Structure Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  31. Key Co-Crystal Structure D9N7ʹ Co-Crystal Structure Steric Barrier Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  32. Monomer Summary Isotropic Mesophase • Mesophase/Isotropic: D‒A Interaction • Crystalline: Side Chain Interaction • Branched NDI: D‒A Retention • Branched DAN: D‒A Separation • N7ʹR: No Observed Mesophase Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  33. Monomer Summary • Mesophase/Isotropic: D‒A Interaction • Crystalline: Side Chain Interaction • Branched NDI: D‒A Retention • Branched DAN: D‒A Separation • N7ʹR: No Observed Mesophase Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  34. Monomer Summary • Mesophase/Isotropic: D‒A Interaction • Crystalline: Side Chain Interaction • Branched NDI: D‒A Retention • Branched DAN: D‒A Separation • N7ʹR: No Observed Mesophase Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  35. Monomer Summary • Mesophase/Isotropic: D‒A Interaction • Crystalline: Side Chain Interaction • Branched NDI: D‒A Retention • Branched DAN: D‒A Separation • N7ʹR: No Observed Mesophase Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  36. Monomer Summary • Mesophase/Isotropic: D‒A Interaction • Crystalline: Side Chain Interaction • Branched NDI: D‒A Retention • Branched DAN: D‒A Separation • N7ʹR: No Observed Mesophase Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  37. Monomer Summary Tunable Phase Transitions Tunable Thermochromic Behavior Alvey, P. M.; Lynch, V.; Reczek, J.J.; Iverson, B.L. J. Org. Chem. 2010, 75, 7682.

  38. NDI in the Literature • Photovoltaic Materials • Semiconductors • Anion Sensors • Molecular Self-Assembly • DNA Intercalation • Electronic Push/Pull Systems For New Small Molecules and Polymers Würthner & Matile Scifinder Substructure Search Results of NDI. J. Org. Chem. 2006, 71, 8098. J. Org. Chem. 2008, 73, 738.

  39. NDI Functionalization Odobel, F. J. Mater. Chem. 2007, 17, 4139.

  40. Conjugated NDI-Donor Polymers Low Lying LUMO • Notable Properties • Conjugation - Charge Transport • Tunable Electronic Properties • n-Type Character • Solubilizing Side Chains • Easily Processed (spin coat) • Applications • Organic Semiconductors • Bulk Heterojunction Solar Cells HOMO Dependent on Donor Bhosale, S.; Bhosale, S.; Bhargava, S. Org. Biol. Chem. 2012, 10, 6455.

  41. Scientific Question • How will donors with different aromatic sizes and electrostatic • potentials affect the overall stacking morphology of conjugated • NDI‒donor polymer chains? ? Face-Centered Intermolecular (D‒A) Offset Face-to-Face

  42. Investigated Polymers Spartan Models Using the DFT B3LYP G-31* Method Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  43. Polymer Synthesis 20 16-19 12 16 PB 9 13 17 PN 10 14 18 PD 15 11 19 PA Alvey, P. M.; Iverson, B. L. Org. Lett. 2012, 14, 2706. Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  44. Optical & Electronic Properties PB = black PN = red PD = purple PA = teal Normalized Film Normalized CHCl3 4×10-6 M CHCl3 Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  45. Optical & Electronic Properties PB = black PN = red PD = purple PA = teal Normalized Film Normalized CHCl3 4×10-6 M CHCl3 Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  46. Optical & Electronic Properties PB = black PN = red PD = purple PA = teal Normalized Film Normalized CHCl3 4×10-6 M CHCl3 Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  47. Optical & Electronic Properties PB = black PN = red PD = purple PA = teal Normalized Film Normalized CHCl3 0 Intermolecular D‒A Interaction or Intramolecular Charge-Transfer? 4×10-6 M CHCl3 Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  48. Interchain Stacking PB = black PN = red PD = purple PA = teal X-Ray Powder Diffraction PB PD PN PA 48 Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  49. Interchain Stacking Model Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

  50. Interchain Stacking Model Models Not Supported by XRD Data Alvey, P. M.; Ono, R. J..; Bielawski, C. W.; Iverson, B.L. Macromolecules, 2013, 46, 718.

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