Developing the synthetic control required for the intentional 3-D arrangement of
atoms remains a holy grail in crystal engineering and materials chemistry. The explosive
development of metal-organic materials in recent decades has shed light on the above
problem. Their properties can be tuned by varying the organic and/or inorganic building
units. In addition, their crystallinity makes it possible to determine their structures via
the X-ray diffraction method. This dissertation will focus on the chemistry and
applications of two kinds of metal-organic materials, namely, metal-organic frameworks
(MOFs) and metal-organic polyhedra (MOP).
MOFs are coordination polymers. Their permanent porosity makes them a good
“gas sponge”. In the first section, an isoreticular series of MOFs with dendritic hexacarboxylate
ligands has been synthesized and characterized structurally. One of the
MOFs in this series, PCN-68, has a Langmuir surface area as high as 6033 m2 g-1. The
MOFs also possess excellent gas (H2, CH4, and CO2) adsorption capacity.
In the second section, a NbO-type MOF, PCN-46, was constructed based on a
polyyne-coupled di-isophthalate linker formed in situ. Its lasting porosity was confirmed by N2 adsorption isotherm, and its H2, CH4 and CO2 adsorption capacity was examined
at 77 K and 298 K over a wide pressure range (0-110 bar).
Unlike MOFs, MOP are discrete porous coordination nanocages. In the third
section, a MOP covered with bulky triisopropylsilyl group was synthesized, which
exhibits a thermosensitive gate opening property. This material demonstrates a
molecular sieving effect at a certain temperature range, which could be used for gas
separation purpose.
In the last section, a MOP covered with alkyne group was synthesized through
kinetic control. The postsynthetic modification via click reaction with azide-terminated
polyethylene glycol turned them into metallomicelles, which showed controlled release
of an anticancer drug 5-fluorouracil.
In summary, two kinds of metal-organic materials have been discussed in this
dissertation, with the applications in gas storage, gas separation, and drug delivery.
These findings greatly enrich the chemistry and applications of metal-organic materials.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2010-12-8677 |
| Date | 2010 December 1900 |
| Creators | Zhao, Dan |
| Contributors | Zhou, Hongcai |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | thesis, text |
| Format | application/pdf |
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