Title

Solid state chemistry: Structural influences of the binucleating transition metal/tetra-2-pyridylpyrazine complex on the molybdophosphonate and molybdoarsonate class of materials

Date of Award

2004

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor(s)

Jon Zubieta

Keywords

Binucleating, Molybdophosphonate, Molybdoarsonate, Pyridylpyrazine-tetra-2

Subject Categories

Chemistry | Physical Sciences and Mathematics

Abstract

Rational design synthesis in inorganic-organic hybrid materials has proven elusive. While the hydrothermal method provides a route that affords single crystalline products that are easily characterized, the multitude of reaction variables as well as the inability to view the reaction at maximum temperature, offers little insight into the mechanistic understanding of product formation. Considering the immensity of the oxide domain, it is important to focus on a few related reaction systems, in this case the molybdenum phosphonates and the molybdenum arsonates. By utilizing subtle changes in starting materials I was able to synthesis numerous compounds with similar building blocks. The best examples of recurring building blocks are seen in chapters two and three with the Mo 5 O 15 (O 3 PR) 2 and Mo 6 O 18 (O 3 AsR) 2 clusters, respectively.

All compounds were synthesis hydrothermally and characterized by single-crystal x-ray diffraction. The structures discussed herein range from the rather simplistic one-dimensional chain [{Cu 2 (tpypyz)(H 2 O)} 2 (Mo 3 O 8 ) 2 (O 3 PCH 2 PO 3 ) 3 ] 16.9H 2 O to the much more complex three-dimensional [{Ni 2 (tpyprz)(H 2 O) 2 }(Mo 3 O 8 ) 2 (O 3 PCH 2 PO 3 ) 2 ]. Individually, each structure merely represents a novel compound, together they start to reveal knowledge about the structural preferences and coordination tendencies that are critical if one expects to someday gain mechanistic control over this domain.

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