PREPARATION AND INVESTIGATION OF GROUP 13 METAL ORGANO- PHOSPHATE HYBRID-FRAMEWORK MATERIALS By YUE ZHAO A Dissertation Submitted to the Graduate Faculty of WAKE FOREST UNIVERSITY GRADUATE SCHOOL OF ARTS AND SCIENCES in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY In the Department of Chemistry May 2009 Winston-Salem, North Carolina Copyright by Yue Zhao 2009 Approved by: Abdessadek Lachgar, Ph. D., Advisor _____________________________ Examining Committee: Natalie A. W. Holzwarth, Ph. D., Chair _____________________________ Christa L. Colyer, Ph. D. _____________________________ Bradley T. Jones, Ph. D. _____________________________ Ronald E. Noftle, Ph. D. _____________________________ ABSTRACT Preparation and Investigation of Group 13 Metal Organo-Phosphate Hybrid-Framework Materials by Yue Zhao Dissertation under the direction of Abdessadek Lachgar, Ph.D., Professor of Chemistry Open-framework materials such as zeolites and low-dimensional materials such as metal phosphates have a wide range of applications in separation processes, catalysis, ion exchange, and intercalation chemistry. Current research in this field is focused on synthesizing hybrid inorganic-organic compounds, which combine inorganic species as nodes and organic species as linkers. These materials have been demonstrated to have versatile structures and show promising properties for applications in the areas of separation, catalysis, magnetism, photo-physics, and electronics. The controlled synthesis of these materials is an ongoing challenge that offers tremendous opportunities in the area of materials science. The objective of the research conducted within the framework of this dissertation is to prepare and characterize hybrid framework metal organo-phosphate materials (MOPs). The idea is to use specific building units that can be linked or modified by functional organic groups to make materials with specific architectures and thus specific properties. The objective is to reach an understanding of how the organic and inorganic pieces fit together to allow for the I preparation of tailor-made materials with specific structures and specific functionality of this type of materials. The synthetic method of choice is a mild hydro- or solvo-thermal method in which the reactants and solvent are sealed in a container and heated slightly above the boiling point of the solvent under autogeneous pressure. Their structural characterization was done by single crystal X-ray diffraction. The presence of the organic moieties was determined by the combination of elemental analysis, XRD and IR spectroscopy. The thermal stability of these materials was determined by a combination of thermogravimetric analysis, IR spectroscopy, and powder XRD. The study has led to the preparation and complete characterization of a number of new MOP materials with novel structures. They show a great diversity of structural topologies, coordination types, dimensionalities, pore sizes and physical or chemical properties. The MOPs synthesized and characterized can be classified in three different types of hybrid frameworks: (1) Hybrid frameworks built of pure inorganic metal phosphates (MPO4) layer or chains linked or coordinated by multitopic organic ligands such as oxalate, 1,10 – phenanthroline and 4,4’-bipyridine. (2) Hybrid frameworks built of metal phosphonates (MPO3R) or metal diphosphonates (MPO3RPO3). In this case the organic functional group is embedded in the inorganic framework. (3) Hybrid frameworks that can be considered to be a combination of the previous two types. They are built of metal phosphonate (MPO3R) layers or chains linked or coordinated by multitopic organic ligands. II DEDICATION To my parents, Tianhua Zhao and Yujun Fang To my wife, Zhihua Yan To my son, Yanxin Matthew Zhao III ACKNOWLEDGEMENTS I would like to express my sincere gratitude to my advisor Dr. Abdessadek Lachgar for his professional guidance, great patience, enthusiasm, and continuous encouragement and support, without which this study could not have been accomplished. I would like to thank my committee members, Dr. Ronald E. Noftle and Dr. Bradley T. Jones for their helpful advice and support during my entire graduate study. I would also like to thank Dr. Cynthia S. Day who not only provided tremendous help in the area of crystallography, but also offered many personal supports. I am grateful to all faculty and staff members of the Department of Chemistry of Wake Forest University for creating a positive learning environment. I would also like to thank Mike Thompson on tremendous help not only in the lab, but also in the personal life. I am grateful to all the former and current group members: Postdocs (Dr. Duraisamy Thirumalai, Dr. Valan C. Amburose, Dr. Bangbo Yan, Dr. Mostafa Taibi, and Dr. Jianjun Zhang); Graduate students (Ekatherina Anokhina, Huajun Zhou, Zhihua Yan, Sergio Aaron Gamboa, and Lei Chen); and Undergraduate students (Yumi Okuyama, Greg Becht, Julien Cosqueric, Barry J. Davis Jr., Mallory Hackbarth and Jenny Nesbitt). Your help and cooperation will always be in my memory. I would like to thank those who have collaborated with our group. Dr. Jochen Glaser (University of Tübingen, Germany) and Dr. Kenneth J. Brown (Winston Salem State University) helped me during their brief research stay within our group. IV TABLE OF CONTENTS Abstract I Dedication III Acknowledgements IV Table of Contents V List of Tables VIII List of Figures XI Chapter 1. Introduction 1 1.1 Materials with Extended Framework 2 1.2 Selected Applications of Open Framework Materials 3 1.3 Metal Phosphate Inorganic Materials 5 1.4 Metal Organic Framework Materials 7 1.5 Metal organo-Phosphate Materials (MOPs) Chemistry 7 1.6 Research Objective 12 1.7 Rationale for Choosing the Building Units 14 1.8 Synthetic Strategies 19 2. Experimental Techniques 23 2.1 Methods of Synthesis 24 2.2 Chemicals Used 26 2.3 Methods of Characterization 28 3. Synthesis, Crystal Structures and Characterization of MOP1 31 3.1 Introduction 32 V 3.2 General materials and methods 32 3.3 Gallium phosphate oxalates 33 3.3.1 Hydrothermal synthesis 34 3.3.2 Crystal structure determination 36 3.3.3 Results and discussion 41 3.4 Indium phosphate oxalates 50 3.4.1 Hydrothermal synthesis 50 3.4.2 Crystal structure determination 52 3.4.3 Results and discussion 57 3.5 Gallium arsenate oxalate 68 3.5.1 Hydrothermal Synthesis 68 3.5.2 Crystal structure determination 69 3.5.3 Results and discussion 72 4. Synthesis, Crystal Structures and Characterization of MOP2 76 4.1 Introduction 77 4.2 Experimental section 78 4.3 Crystal structure determination 81 4.4 Results and discussion 87 5. Synthesis, Crystal Structures and Characterization of MOP3 96 5.1 Introduction 97 5.2 General materials and methods 97 5.3 Neutral gallium methyl-phosphonate oxalates 98 5.3.1 Hydrothermal synthesis 99 VI 5.3.2 Crystal structure determination 100 5.3.3 Results and discussion 105 5.4 Intercalation of gallium phosphonate oxalates 117 5.4.1 Solvothermal synthesis 118 5.4.2 Crystal structure determination 120 5.4.3 Results and discussion 127 6. Conclusions 136 References 140 Appendix 157 Scholastic Vita 181 VII LIST OF TABLES Table 2.1 List of Chemicals 26 Table 3.1 Crystallographic Data of MOP1-1 and MOP1-2 37 Table 3.2 Most important bond lengths (Å) and angles (degree) for compound MOP1-1: [Ga4(PO4)4(H2PO4)(C2O4)]( C4N3H15)(H2O)2.5 39 Table 3.3 Most important bond lengths (Å) and angles (degree) for compound MOP1-2: [Ga8(H2O)4(PO4)4(HPO4)4(C2O4)4](C10N4H28)(H2O)4 40 Table 3.4 Crystallographic Data of MOP1-3 and MOP1-4 53 Table 3.5 Most important bond lengths (Å) and angles (degree) for compound MOP1-3: [In6(HPO4)8(C2O4)3]( C10N4H28) 55 Table 3.6 Most important bond lengths (Å) and angles (degree) for compound MOP1-4: [In4(HPO4)6(C2O4)2]( C10N4H28)(H2O)2 56 Table 3.7 Hydrogen Bond Lengths (Å) and Angles (degree) for Compound MOP1-4 57 Table 3.8 Crystallographic Data of MOP1-5 70 Table 3.9 Most important bond lengths (Å) and angles (degree) for compound MOP1-5: [Ga6(OH)2(AsO4)2(HAsO4)4(C2O4)3](C10N4H28)·(H2O)3.5 71 Table 4.1 Crystallographic Data of MOP2 compounds 82 Table 4.2 Most important bond lengths (Å) and angles (º) for compound MOP2-1: Ga(H2O)(PO3CH2PO3)(C6H14N2)0.5 84 Table 4.3 Hydrogen Bond Lengths (Å) and Angles (degree) for Compound MOP2-1 84 VIII Table 4.4 Summary of Bond Lengths (Å) and Angles (degree) for Compound MOP2-2: Ga(PO3CH2PO3H)[(PO3H)2CH2](C2N2H10) 85 Table 4.5 Hydrogen Bond Lengths (Å) and Angles (degree) for Compound MOP2-2 85 Table 4.6 Summary of Bond Lengths (Å) and Angles (degree) for Compound MOP2-3: Ga(C12H8N2)[(PO3H)2CH2](PO3HCH2PO3H2)[(PO3H1.5)2CH2](C12H9N2) 86 Table 4.7 Hydrogen Bond Lengths (Å) and Angles (degree) for Compound MOP2-3 93 Table 5.1 Crystallographic Data of MOP3-1 and MOP3-2 101 Table 5.2 Most important bond lengths (Å) and angles (degree) for compound MOP3-1: [Ga(H2O)(PO3CH3)(C2O4)0.5](H2O) 103 Table 5.3 Most important bond lengths (Å) and angles (degree) for compound MOP3-2: Ga(H2O)(PO3CH3)(C2O4)0.5 103 Table 5.4 Hydrogen Bond Lengths (Å) and Angles (degree) for Compound MOP3-1 and MOP3-2 104 Table 5.5 Layered gallium phosphonate oxalates intercalated by different SDAs 117 Table 5.6 Crystallographic Data of MOP3-3 and MOP3-4 121 Table 5.7 Crystallographic Data of MOP3-5 and MOP3-6 122 Table 5.8 Most important bond lengths (Å) and angles (degree) for 2D compound MOP3-3, MOP3-4 and MOP3-5: Ga3(PO3CH3)4(C2O4)(SDA)(solvent) 124 IX Table 5.9 Most important bond lengths (Å) and angles (degree) for 1D