Title page for ETD etd-04172009-155646


Type of Document Dissertation
Author Hu, Liangming
Author's Email Address lmhu@vt.edu
URN etd-04172009-155646
Title Inorganic-Organic Hybrid Networks Constructed from Different Metal Ions and Ligands
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Hanson, Brian E. Committee Chair
Angel, Ross J. Committee Member
Gandour, Richard D. Committee Member
Merola, Joseph S. Committee Member
Slebodnick, Carla Committee Member
Keywords
  • hybrid networks
  • hydrothermal synthesis
  • templates
  • ligands
  • transition metal ions
Date of Defense 2009-04-15
Availability unrestricted
Abstract
Hybrid inorganic-organic networks have been studied in both chemistry and materials science due to properties, (e.g. porosity, magnetic and electronic behaviors) that may lead to applications in catalysis, gas absorption and storage. It is important to understand the different structural topologies shown by hybrid networks to help develop practical applications for these materials. The research is focused on the design and synthesis of well-defined hybrid network structures that have potential to contain molecular size cavities that can be used for catalysis and gas storage.

In the field of organic-inorganic hybrid networks, the goals are to design and synthesize 1D, 2D and 3D networks with cavities, and to characterize them by X-ray, TGA and surface area measurements. Twenty-six networks have been successfully made with interesting structure topologies. These hybrid network structures are classified into three series based on their ligands. Series I contains ten hybrid networks constructed from the flexible ligand, 4, 4’-trimethylenedipyridine¬ (TMDP),¬ Zn2+ ions, and H3PO3, and with aromatic alcohols as templates to direct the formation of various hybrid network structures. Series II consists of five structures constructed from the relatively rigid ligand, 4, 4’-bisimidazolelybipyridine (BIB)¬¬ with metal ions (Cu2+, Ni2+) and the conjugated bases of H3PO3 and H3PO4. The BIB ligand is not commercially available so is produced and characterized by NMR, mass spectrometry and TGA. Rigid network structures were expected to construct with pores of molecular dimensions with the BIB ligand. To date, the BIB ligand has not yield the desired porous network, however, these 3D hybrid networks have interesting topologies, one of which is an interdigitated network that is the precursor for 3D interpenetrated networks. Series III contains five hybrid structures constructed from various organic ligands, such as tartaric acid, picolinic acid and 1, 2, 4-triazole. In addition to the hybrid networks, six hydrogen bonded networks were prepared. Graph-Analysis is applied to study these hydrogen bonded network structures. The π….π interaction is also discussed within the hydrogen bonded networks.

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