Graduation Year

2018

Document Type

Dissertation

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Chemistry

Major Professor

Shengqian Ma, Ph.D.

Committee Member

Jianfeng Cai, Ph.D.

Committee Member

Babu Joseph, Ph.D.

Committee Member

Julie P. Harmon, Ph.D.

Keywords

Azamacrocycles, Coordination Polymer, Porous Materials, Sensing

Abstract

Research in metal-organic frameworks (MOFs) has risen greatly in recent decades Owing to their unequaled potential tunability and structural diversity. MOFs may be described as crystalline structures composed of metal cations or clusters of cations, commonly referred to as secondary building units (SBUs), and custom-designed organic ligands. The variety of structural motifs, ligands, and SBUs that may be incorporated promote the attainment of essentially countless potential MOFs and application in numerous areas of interest, such as gas adsorption, catalysis, gas separation, and sensing. Further functionalization of MOF materials by means of post-synthetic modification(PSM)33–37 of metal clusters or organic ligands, constructing frameworks using functional ligands or metal clusters, and incorporating advantageous molecules including organometallic molecules,38–41 enzymes,42–45 metal nanoparticles (NPs),8,46–48 heteropolyacids49–51 within the pores advance the diverse number of species, including organic ligands, inorganic metal ions/clusters, and guests, used to construct MOFs materials lead to MOFs materials possessing phenomenal properties. Implementation of these materials in sensing arises from the frameworks’ characteristic ability to increase the concentration of a desired analyte to a greater degree than its overall presence within the system; imparting an inherent sensitivity to the aforementioned analyte. MOFs materials also possess the potential for selectivity for specific analytes or classes of analytes through mechanisms such as size exclusion (molecular sieving), chemically specific interactions between the adsorbate and framework, and the directed design of pore and aperture size through the selection of appropriate organic linkers or struts.

Flexible azamacrocycle-based ligands are constructed through the use of pliable carboxylate pendant arms and azamacrocycles, e.g cyclen and tacn, and used in the pursuit of novel metal macrocycle frameworks (MMCF). Polyazamacrocycles represent a popular class of macrocyclic ligands for supramolecular chemistry and crystal engineering. This popularity may be due to their complexes’ high thermodynamic stability, relative kinetic inertness, basicity, transition metal-ion coordinating ability and rigid structure. Furthermore, their utilization promotes intriguing network topologies as coordination in complexes containing tetradentate azamacrocycles generally produces only two isomers differing via the coordination ligand’s conformation. The highly reported equatorial N4¬ ¬coordination of the macrocycle allows for interaction at the two vacant trans-axial positons, whilst the folded conformations permits interaction at two vacant cis positions. Azamacrocycle complexes differ from those of other classes of macrocycles due to the fact the macrocyclic cavity is commonly occupied by metal cations. Materials containing azamacrocycles have found use in applications such as bleaching and oxidative catalysis and molecular recognition. Cyclen units have reportedly been incorporated to construct pH-dependent selective receptors for copper (II), zinc(II), yttrium(III), and lanthanum(III) ions. Herein, we describe the synthesis and characterizations of a new lanthanide framework, La(C40H40N4O8)(NH2(CH2)2)NO3 or MMCF-3, which retains a vacancy in the macrocycle unit encourages the utilization of the framework as a cation receptor and precursor for heterometallic frameworks. The inclusion of azamacrocycles into MOF materials combine the characteristic high thermodynamic stability, basicity, and strong metal complexation of the macrocycles with the high porosity, surface area, and tunability of the frameworks. Full realization of the potential of Azamacrocyclic-based MOFs requires the preparation of new entrants to this class of materials that espouse various topological structures while incorporating diverse azamacrocycles. It has been shown that the hierarchical porosity associated with macrocyclic based frameworks can be obtained using this class of ligands.71,99 The development of more frameworks exhibiting this characteristic is needed to fully investigate the potential applications of MOFs retaining the vacant cavities of the azamacrocycles. Effectuation of hierarchical porosity of azamacrocyclic frameworks will broaden sensing applications, e.g. azamacrocycles have performed as receptors of anions, cations, amino acids and other analyte molecules, and provide an ideal slot to integrate open metal site into MOFs.

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