W&M ScholarWorks Undergraduate Honors Theses Theses, Dissertations, & Master Projects 2009 Structure and Luminescence of Copper(I) Cyanide Networks Incorporating Monoamine, Diamine, and Monoimine Ligands Amanda Noelle Ley College of William and Mary Follow this and additional works at: https://scholarworks.wm.edu/honorstheses Part of the Chemistry Commons Recommended Citation Ley, Amanda Noelle, "Structure and Luminescence of Copper(I) Cyanide Networks Incorporating Monoamine, Diamine, and Monoimine Ligands" (2009). Undergraduate Honors Theses. Paper 563. https://scholarworks.wm.edu/honorstheses/563 This Honors Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Undergraduate Honors Theses by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. Structure and Luminescence of Copper(I) Cyanide Networks Incorporating Monoamine, Diamine, and Monoimine Ligands TABLE OF CONTENTS Acknowledgements .......................................................................................................... iv List of Figures .....................................................................................................................v List of Tables and Charts .............................................................................................. vii Abstract ........................................................................................................................... viii Introduction ........................................................................................................................1 Metal-Organic Networks ..................................................................................................1 Properties of Copper(I) .....................................................................................................2 Copper(I) Cyanide Networks ...........................................................................................2 Luminescence .................................................................................................................11 Experimental ....................................................................................................................15 Materials and Methods ...................................................................................................15 General Analyses ............................................................................................................15 X-Ray Analysis ..............................................................................................................15 N-Benzylpiperazine (BzPip) Synthesis ..........................................................................16 N,N’-Dibenzylpiperazine (Bz2Pip) Synthesis ...............................................................16 General Method of Aqueous Reflux Synthesis ..............................................................17 General Method for HT Reactions .................................................................................17 General Method for Pressure Tube Reactions ................................................................22 General Method for Vapor Diffusion Studies ................................................................28 Results and Discussion .....................................................................................................29 Synthesis .........................................................................................................................29 Characterization of Networks Containing Diamine Ligands .........................................30 Networks Displaying 2CuCN: 1L Ratios ...................................................................32 Networks Displaying Higher Order CuCN:L Ratios..................................................35 Characterization of Networks Containing Monoimine Ligands ....................................41 CuCN 2-Picoline Networks ........................................................................................43 ii CuCN 3-Ethylpyridine Network.................................................................................44 CuCN 4-tert-Butylpyridine Network .........................................................................46 CuCN 1-Methylimidazole Network ...........................................................................47 Characterization of Networks Containing Monoamine Ligands ...................................47 CuCN N,N’-Dimethylcyclohexylamine Network ......................................................49 CuCN Piperidine Networks ........................................................................................50 CuCN N-Methylmorpholine Network ........................................................................51 Luminescent Behavior of Networks Containing Diamine Ligands ...............................52 Luminescent Behavior of Networks Containing Monoamine and Monoimine Ligands ............................................................................56 Conclusion ........................................................................................................................67 References .........................................................................................................................69 Appendix A: Crystallographic Data...............................................................................71 iii Acknowledgements I would like to thank Dr. Robert Pike for his endless patience and guidance throughout the process of writing this thesis, as well as for all of the guidance he has given me over the past four years. I would also like to thank the remaining members of my committee, Dr. John C. Poutsma, Dr. Deborah C. Bebout, and Dr. M. Christine Porter for dedicating their time in considering this thesis. I am eternally grateful to my “lab partner” and research comrade, Jake Kuperstock, who helped me retain my sanity throughout these past four years. For the past four years, I have had the incredible privilege of working with the entire William and Mary Chemistry department, and have gained so much knowledge and so many skills that will stick with me for the rest of my life. I am thankful for my family, who are the most incredible and encouraging people I have ever known and believed in me even when I didn’t. I thank the generous donors of the Petroleum Research Fund of the American Chemical Society (44891-B3) and the Jeffress Memorial Trust (#J-678) as well as the Howard Hughes Medical Institute. Finally, I am thankful for the support of the National Science Foundation (CHE- 0443345), which allowed for the purchase of the X-Ray Diffractometer, and the College of William and Mary. iv List of Figures Figure Page 1. Structure of the Cyanide Anion.........................................................................3 2. X-Ray Crystal Structure and Powder Diffraction Pattern of CuCN..................4 3. X-ray crystal structure of (CuCN)3(Pyz)...........................................................5 4. X-ray crystal structure of (CuCN)3(Pyz)2..........................................................5 5. X-ray crystal structure of (CuCN)2(Me2Pip).....................................................6 6. X-Ray Crystal Structure of (CuCN)2(2Pic)3......................................................7 7. X-Ray Crystal Structure of (CuCN)2(4Pic)3......................................................8 8. X-Ray Crystal Structure of (CuCN)2(Py)..........................................................8 9. Electronic Transitions......................................................................................13 10. TGA trace of (CuCN)4(Me2Pip)......................................................................31 11. X-ray Crystal Structure of (CuCN)2(Bz2Pip)..................................................33 12. X-ray structure of (CuCN)2(Ph2CHPip)..........................................................34 13. X-ray Crystal Structure of (CuCN)20(Pip)7......................................................36 14. X-ray Crystal Structure of (CuCN)4(EtPip)....................................................37 15. X-ray crystal structure of (CuCN)4(Me2Pip)..................................................38 16. X-ray crystal structure of (CuCN)4(Et2Pip)....................................................39 17. X-ray Crystal Structure of (CuCN)3(BzPip)2..................................................40 18. X-ray Crystal Structure of (CuCN)4BzPip......................................................41 19. X-Ray Crystal Structure of (CuCN)(2Pic).......................................................43 20. X-Ray Crystal Structure of (CuCN)2(3EtPy)3.................................................45 t 21. X-Ray Crystal Structure of (CuCN)2(4 BuPy)3...............................................46 v 22. X-Ray Crystal Structure of (CuCN)(1MeIm)3...............................................47 23. TGA Trace of (CuCN)(NEt3)..........................................................................48 24. X-ray Crystal Structure of (CuCN)(NMe2Cy).................................................49 25. X-ray Crystal Structure of (CuCN)3(Pipd)4.....................................................50 26. X-ray Crystal Structure of (CuCN)(MeMorph)...............................................52 27. Luminescence Spectra of CuCN at 298 K.......................................................54 28.