Document Type


Date of Degree

Spring 2010

Degree Name

PhD (Doctor of Philosophy)

Degree In


First Advisor

MacGillivray, Leonard R

First Committee Member

Pigge, Christopher

Second Committee Member

Bowden, Ned B

Third Committee Member

Cheatum, Christopher M

Fourth Committee Member

Olivo, Horacio F


Chemistry is on the verge of a new era where the attention of chemists has shifted from covalent bonds to noncovalent interactions and their use as a predictable way to guide reactions pathways and product formation. Nature synthesizes elegant molecules under mild conditions and the designed syntheses have been demonstrated to be largely dependent on recognition, self-assembly and templating effects between molecular building blocks. Although covalent synthesis in fluidic medium via supramolecular control has been achieved with limited success, organic solid state has been of particular interest since it avoids solvent effects, and is able to provide unique materials with remarkable stereoselectivity under environment-friendly conditions. Although reactions in solids have resulted in a number of remarkable discoveries in chemistry and materials science, solid-state synthesis is generally not considered as a mainstream synthetic medium and solid-state reactions are seldom appreciated as an efficient way to access molecular targets. Owing to the limited number of solid-state reactions and the uncontrollable nature of crystal packing, solid state has not been utilized readily as a primary synthetic medium. In this context, reactions conducted in multicomponent molecular assemblies or co-crystals have been attracting much attraction in recent years as a general way of controlling the reactivity of molecules in solid state. A molecular component in the multicomponent molecular solid, acting as a linear template, has been shown to preorganize molecules in a modular way via intermolecular interactions and engineer their physical and/or chemical properties. The [2+2]photodimerization of olefins is a successful demonstration how templated solid state synthesis can efficiently synthesize complex targets that are synthetically challenging via conventional routes. In this dissertation, the generality and synthetic applicability of the templated synthetic approach in solid state will be described. How supramolecular interactions in molecular co-crystals precisely guide covalent bond formation in order to construct complex molecular targets will be demonstrated. Finally, co-crystallization will be shown as a general way to control optical properties in crystals.


Cocrystal, Organic Synthesis, Solid State, Supramolecular, Template-directed


xix, 185 pages


Includes bibliographical references (pages 162-167).


Copyright 2010 Saikat Dutta

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