New Jersey Institute of Technology Digital Commons @ NJIT Dissertations Electronic Theses and Dissertations Spring 5-31-2012 Synthesis, molecular and solid state structures, and magnetic properties of sandwich lanthanide phthalocyanines lacking C-H bonds Wycliffe A. Graham New Jersey Institute of Technology Follow this and additional works at: https://digitalcommons.njit.edu/dissertations Part of the Materials Science and Engineering Commons Recommended Citation Graham, Wycliffe A., "Synthesis, molecular and solid state structures, and magnetic properties of sandwich lanthanide phthalocyanines lacking C-H bonds" (2012). Dissertations. 319. https://digitalcommons.njit.edu/dissertations/319 This Dissertation is brought to you for free and open access by the Electronic Theses and Dissertations at Digital Commons @ NJIT. It has been accepted for inclusion in Dissertations by an authorized administrator of Digital Commons @ NJIT. For more information, please contact [email protected]. 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Please Note: The author retains the copyright while the New Jersey Institute of Technology reserves the right to distribute this thesis or dissertation Printing note: If you do not wish to print this page, then select “Pages from: first page # to: last page #” on the print dialog screen The Van Houten library has removed some of the personal information and all signatures from the approval page and biographical sketches of theses and dissertations in order to protect the identity of NJIT graduates and faculty. ABSTRACT SYNTHESIS, MOLECULAR AND SOLID STATE STRUCTURES, AND MAGNETIC PROPERTIES OF SANDWICH LANTHANIDE PHTHALOCYANINES LACKING C-H BONDS by Wycliffe A. Graham A new class of sandwich phthalocyanine (Pc) compounds without C-H bonds was synthesized and characterized. They are the bis[octakis(perfluoro i-C3F7) octakis(perfluoro)phthalocyaninato(2−)]M(III) complexes, formulated as (F64Pc)2MH, M = Tb, Dy, Lu, Y. Single molecular magnetic (SMM) behavior in the (F64Pc)2TbH and (F64Pc)2DyH complexes was confirmed through slowed relaxation response of their magnetization in an applied time varying magnetic field during alternating current (AC) magnetic testing in the range 2 - 50 K. The energy barrier to magnetic reversal, ∆ = 215 −1 −1 7 −1 cm and the pre-exponential factor, τ0 = 2.7 x 10 s were estimated for the undiluted (F64Pc)2TbH with direct current bias magnetic field (Hdc) of 1000 Oe applied. −1 −1 5 −1 Undiluted (F64Pc)2DyH gave estimated values of ∆ = 31 cm and τ0 = 1.6 x 10 s at Hdc = 500 Oe. These respective values are within the range observed for the unsubstituted Tb and Dy analogues. Magnetic hysteresis testing at 0.04 K exhibited hysteresis in both of these complexes. Magnetic circular dichroism (MCD) tests on (F64Pc)2Tb frozen in acetone at 1.8-1.9 K exhibited a “butterfly shaped” hysteresis which appeared to depend on the oxidation state of the complex and which also provided evidence of quantum tunneling of magnetization. The chemical tuning of the Pc macrocycle of these complexes through the replacement of the H atoms with the electron withdrawing fluorine atom and i-C3F7 group has created additional functionalities. Thermal analysis in the forms of thermogravimetric analysis and differential scanning calorimetry showed the complexes to be stable up to 450°C in air and N2. Cyclic voltammetry revealed four reduced and one oxidized states, the oxidized state occurring at > 1.2 V, showing the complexes’ resistance to oxidation. The (F64Pc)2MH compounds − derive their uniqueness as [(F64Pc)2M] sandwich phthalocyanine complexes with exceptional thermal and oxidative stability. SYNTHESIS, MOLECULA R AND SOLID STATE STRUCTURES, AND MAGNETIC PROPERTIES OF SANDWICH LANTHANIDE PHTHALOCYANINES LACKING C-H BONDS by Wycliffe A. Graham A Dissertation Submitted to the Faculty of New Jersey Institute of Technology in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Materials Science and Engineering Interdisciplinary Program in Materials Science and Engineering May 2012 Copyright © 2012 by Wycliffe A. Graham ALL RIGHTS RESERVED APPROVAL PAGE SYNTHESIS, MOLECULAR AND SOLID STATE STRUCTURES, AND MAGNETIC PROPERTIES OF SANDWICH LANTHANIDE PHTHALOCYANINES LACKING C-H BONDS Wycliffe A. Graham Dr. Joseph Bozzelli, Dissertation Co-Advisor Date Distinguished Professor of Chemistry and Environmental Science, NJIT Dr. Trevor Tyson, Dissertation Co-Advisor Date Distinguished Professor of Physics, NJIT Dr. Nuggehalli Ravindra, Committee Chairman Date Professor of Physics, NJIT Dr. Steve Greenbaum, Committee Member Date Professor of Physics, Hunter College, CUNY, New York Dr. Keun Ahn, Committee Member Date Assistant Professor of Physics, NJIT Dr. Haidong Huang, Committee Member Date Assistant Professor of Chemistry and Environmental Science, NJIT iv BIOGRAPHICAL SKETCH Author: Wycliffe A. Graham Degree: Doctor of Philosophy Date: January 2012 Undergraduate and Graduate Education: • Doctor of Philosophy in Materials Science and Engineering, New Jersey Institute of Technology, Newark, NJ, 2012 • Master of Philosophy (M.Phil.) in Physics, University of the West Indies, Mona, Jamaica West Indies, 1989 • Bachelor of Science in Natural Sciences, University of the West Indies, Mona, Jamaica West Indies, 1983 Professional Education • Construction Technology and Management, The Chartered Institute of Building, Englemere, U.K., 1992 Major: Materials Science and Engineering Presentations and Publications: Pinnock, W.R.; Graham, W. A., Radioactivity in Jamaican Bauxite Waste, in Bauxite Tailings, Proceedings of an International Conference on Bauxite Waste, Kingston, Jamaica, Eds. Wagh, A.S.; Desai. P., 1986,113-117. Graham, W.A., Building Materials Standards in Jamaica Today, JB I Journal, 10 Graham, W.A., Aggregates for Concrete, Builder’s Magazine, Jamaica , 1995, 7, 13 – 17. v Graham, W.A., New Monitoring Procedures for Aggregates Used in Concrete, in Proceedings of the Quarry Operators Seminar, Kingston, Jamaica, 25-33. Graham, W.A., Phthalocyanine Synthesis, Poster presentation at th CUNY-AGEP 11 Annual CUNY Conference in Science and Engineering, New York, 2008 Graham, W.A.; Gorun, S.M. Synthesis, X-ray Structures and Magnetic Properties of the first fluorophthalocyanine sandwich complexes. Poster presentation at Targeted Fellowship Luncheon, NJIT. 2008. Graham, W.A.; Gorun, S.M. Magnetism in Some bis[octakis(perfluoro i-C3F7) (perfluoro)phthalocyninato] M(III) Complexes, Oral presentation at the CUNY-AGEP 13th Annual CUNY Conference in Science and Engineering, New York, 2010 Graham, W.A.; Gorun, S.M., Synthesis, X-ray Structures and Magnetism of Lanthanide Sandwich complexes with H-Free, Internally Stabilized Closed-Shell Ligands, Manuscript Submitted to Angewandte Chemie, 2011 Liao, M.-S.; Graham, W.; Gorun, S. M.; Huang, M.-J.; Watts, J. D., Electronic Structure, Bonding, And Optical Spectra Of Unsubstituted and Fluorinated Yttrium and Lutetium Bis(Phthalocyanines). 2011; Manuscript in Preparation. Gonidec, M.; Davies, S. E.; Graham, W.; McMaster, J.; Vidal-Gancedo, J.; Gorun, S. M., Slow Magnetic Relaxation Of Highly Reduced States Of A Double-Decker Phthalocyanine Terbium (III) Complex. Barcelona, 2011; Manuscript in Preparation. vi To my family, for their patience, love, support and encouragement. vii ACKNOWLEDGMENT I am indebted to my co-advisors Prof. Trevor Tyson and Prof. Joseph Bozzelli, and former co-advisor Prof. Sergiu Gorun for their guidance, support and mentorship. To the other members of my Ph.D. advisory committee, Prof. N.M. Ravindra, Prof. S. Greenbaum, Prof. K. Ahn and Prof. H. Huang; thank you for agreeing to serve. I wish to acknowledge the assistance of NSF-AGEP, the US Army and the Department of Energy through Argonne National Laboratory, (ANL) for financial support. Dr. R. Lalancette (Rutgers University) and X-M. Lin (ANL) are thanked for the raw X-ray and magnetic data, respectively. Dr. T. Duelks, Bremen University (Germany) is thanked for the Mass Spectroscopy data. My thanks to Dr. S. Greenbaum and Dr. P. Stallworth of the Physics Dept at CUNY for assistance with EPR and Dr. W. Wernsdorfer, Laboratoire de Magnétisme Louis Néel, C.N.R.S., Grenoble France, for magnetic tests and data. Prof. K. Ramanujachary of Rowan University, NJ is thanked for DC magnetism data. Dr. J. Howell of BASi, Indiana, USA is acknowledged for providing us with the initial CV data. The University of Dentistry and Medicine is thanked for the use of their DSC machine and Dr. Brukh at Rutgers University, Newark for the use of their NIR and MS machines. The author appreciates the significant assistance of collaborators Dr. J. D. Watts, Dr. M-S. Liao and co-workers at Jackson State University, Mississippi, on DFT/TDDFF; Dr. J. Veciana, Dr.