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Interplay Between Structure and Properties in Dicyanoaurate-Based Coordination Polymers

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Interplay Between Structure and Properties in Dicyanoaurate-Based Coordination Polymers INTERPLAY BETWEEN STRUCTURE AND PROPERTIES IN DICYANOAURATE-BASED COORDINATION POLYMERS by Julie Lefebvre B.Sc, McGill University, 2002 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in the Department of Chemistry © Julie Lefebvre 2008 SIMON FRASER UNIVERSITY Spring 2008 All rights reserved. This work may not be reproduced in whole or in part, by photocopy or other means, without the permission of the author. Library and Bibliotheque et 1*1 Archives Canada Archives Canada Published Heritage Direction du Branch Patrimoine de I'edition 395 Wellington Street 395, rue Wellington Ottawa ON K1A0N4 Ottawa ON K1A0N4 Canada Canada Your file Votre reference ISBN: 978-0-494-46809-8 Our file Notre reference ISBN: 978-0-494-46809-8 NOTICE: AVIS: The author has granted a non­ L'auteur a accorde une licence non exclusive exclusive license allowing Library permettant a la Bibliotheque et Archives and Archives Canada to reproduce, Canada de reproduire, publier, archiver, publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par telecommunication ou par Plntemet, prefer, telecommunication or on the Internet, distribuer et vendre des theses partout dans loan, distribute and sell theses le monde, a des fins commerciales ou autres, worldwide, for commercial or non­ sur support microforme, papier, electronique commercial purposes, in microform, et/ou autres formats. paper, electronic and/or any other formats. The author retains copyright L'auteur conserve la propriete du droit d'auteur ownership and moral rights in et des droits moraux qui protege cette these. this thesis. Neither the thesis Ni la these ni des extraits substantiels de nor substantial extracts from it celle-ci ne doivent etre imprimes ou autrement may be printed or otherwise reproduits sans son autorisation. reproduced without the author's permission. In compliance with the Canadian Conformement a la loi canadienne Privacy Act some supporting sur la protection de la vie privee, forms may have been removed quelques formulaires secondaires from this thesis. ont ete enleves de cette these. While these forms may be included Bien que ces formulaires in the document page count, aient inclus dans la pagination, their removal does not represent il n'y aura aucun contenu manquant. any loss of content from the thesis. Canada APPROVAL Name: Julie Lefebvre Degree: Doctor of Philosophy Title of Thesis: Interplay Between Structure and Properties in Dicyanoaurate-based Coordination Polymers Examining Committee: Chair Dr. Paul C.H. Li Associate Professor, Department of Chemistry Dr. Daniel B. Leznoff Senior Supervisor Associate Professor, Department of Chemistry Dr. Ross H. Hill Supervisor Professor, Department of Chemistry Dr. Gary W. Leach Supervisor Associate Professor, Department of Chemistry Dr. Paul W. Percival Internal Examiner Professor, Department of Chemistry Dr. Jeffrey R. Long External Examiner Associate Professor, Department of Chemistry University of California - Berkeley Date Defended/Approved: March 27, 2008 11 SIMON FRASER UNIVERSITY SFU LIBRARY Declaration of Partial Copyright Licence The author, whose copyright is declared on the title page of this work, has granted to Simon Fraser University the right to lend this thesis, project or extended essay to users of the Simon Fraser University Library, and to make partial or single copies only for such users or in response to a request from the library of any other university, or other educational institution, on its own behalf or for one of its users. The author has further granted permission to Simon Fraser University to keep or make a digital copy for use in its circulating collection (currently available to the public at the "Institutional Repository" link of the SFU Library website <www.lib.sfu.ca> at: <http://ir.lib.sfu.ca/handle/1892/112>) and, without changing the content, to translate the thesis/project or extended essays, if technically possible, to any medium or format for the purpose of preservation of the digital work. The author has further agreed that permission for multiple copying of this work for scholarly purposes may be granted by either the author or the Dean of Graduate Studies. It is understood that copying or publication of this work for financial gain shall not be allowed without the author's written permission. Permission for public performance, or limited permission for private scholarly use, of any multimedia materials forming part of this work, may have been granted by the author. This information may be found on the separately catalogued multimedia material and in the signed Partial Copyright Licence. While licensing SFU to permit the above uses, the author retains copyright in the thesis, project or extended essays, including the right to change the work for subsequent purposes, including editing and publishing the work in whole or in part, and licensing other parties, as the author may desire. The original Partial Copyright Licence attesting to these terms, and signed by this author, may be found in the original bound copy of this work, retained in the Simon Fraser University Archive. Simon Fraser University Library Burnaby, BC, Canada Revised: Fall 2007 Abstract This research project has focused on the design and synthesis of capping ligand-free dicyanoaurate-based coordination polymers. Dicyanoaurate is a building block that readily bridges two transition metals and increases the connectivity of the system through gold-gold interactions. A series of isostructural M(/i-OH2)2[Au(CN)2]2 coordination polymers (Cu, Ni, Co, Fe, Mn) was prepared. Their structure contains an unprecedented motif in which metal centers are doubly bridged by water molecules, generating chains. The mag­ netic interactions present in these water-bridged polymers were investigated; both ferromagnetic (Cu, Ni, Co) and antiferromagnetic interactions (Fe, Mn) were ob­ served. Muon spin relaxation studies showed different magnetic ground states for these polymers, including long-range ordered (Cu, Tc = 0.2 K) and spin-glass states (Ni, Tf = 3.5 K). Several CujA^CN^^analyte)^ polymers (analyte = dimethylsulfoxide, N,N- dimethylformamide, water, pyridine, ammonia) were prepared and found to be vapo- chromic, i.e. change colour upon exposure to volatile analytes. The analyte incorpo­ rated can easily be identified as each colour is specific to one analyte, with maximum reflection ranging from 433 to 560 nm. The infrared cyanide vibration signature of each polymer is also unique and allows another way of identifying the analyte present. The analyte can be exchanged at room temperature, without any thermal treatment. A survey of analyte sensing capabilities was performed by replacing the Cu ions with Ni and Co ions in M[Au(CN)2]2(analyte):E. + The preparation of [cation]{M[Au(CN)2]3} polymers (cation = K+, [PPN] , [nBu4N]+; M = Ni, Co) was also investigated. The incorporation of different cations m affected the structural arrangement of the anionic framework, but did not prevent the 3-D connectivity between the metal centers. Despite the high connectivity, very weak antiferromagnetic interactions were observed which suggests that dicyanoaurate is a poor mediator of magnetic exchange. Studies by transmission electron microscopy showed the presence of trace amounts of NiO and Au nanoparticles in hydrothermally recrystallized samples of dicyanoaurate-containing coordination polymers. These products were hardly de­ tectable by standard analysis techniques, but the NiO nanoparticles dominated the magnetic response at low temperatures. This finding illustrates the care that must be taken when investigating samples prepared by hydrothermal methods. Keywords: coordination polymers; cyanometallate; vapochromism; molecular mag­ netism; gold-gold interactions. IV To those whom I love, To those who cared and understood, To those who offered their support, To the one without whom this would have been impossible, I dedicate this thesis. v The most important thing in science is not so much to obtain new facts as to discover new ways of thinking about them." — Sir William Lawrence Bragg, 1965 "On fait la science avec des faits, comme on fait une maison avec des pierres: mais une accumulation de faits n 'est pas plus une science qu'un tas de pierres n'est une maison." — Henri Poincare, LA SCIENCE ET L'HYPOTHESE , 1905 vi Acknowledgments First and foremost, I would like to thank my senior supervisor, Daniel Leznoff, for his guidance, support, trust and encouragement throughout all these years. His love of chemistry was so great that it was contagious! Learning from him was a pleasure, especially if you could understand his handwriting. I would like to thank my supervisory committee members, Ross Hill and Gary Leach, for their help and support during my degree. Seeing the "big picture" was not always easy, but I'm glad they insisted! A special thank also to Ross for his collaboration and thorough scientific thought process in investigating the formation of nanoparticles impurities. A special thank to my external examiner, Jeffrey Long, for taking the time to read my thesis, being present at my defense and providing useful comments. I would also like to thank Paul Percival, my internal examiner, for carefully reading my whole thesis, giving me useful feedback and teaching me a few grammatical rules! I wish to deeply thank Jeff Sonier not only for performing the muon spin relaxation experiments with us, but also for all his time spent analyzing the data and teaching me about this unusual technique. I'd like to thank the members of his group, especially Fergal Callaghan, Christina Kaiser, Vighen Pacradouni and Pooja Tyagi, for spending numerous hours collecting and analyzing the data over the last five years. I'd like to thank the TRIUMF staff of the Center for Molecular and Materials Science (CMMS) for their 24-hour support during our experiments. I'd like to thank Jim O'Brien, application engineer at Quantum Design, for help­ ing me in my struggles with the SQUID magnetometer, Miki Yang for performing the elemental analysis and Brian Patrick (UBC) for collecting several powder X-ray vn diffractograms over the last two years.
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