Design, synthesis and study of novel supermolecular assemblies.

Format:

Book

Thesis/Dissertation

Author/Creator:

Serrette, Andre Gerard.

Contributor:

Swager, T. M., advisor.

University of Pennsylvania.

Language:

English

Subjects (All):

Chemistry, Inorganic.

0488.

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Local Subjects:

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

0488.

Physical Description:

374 pages

Contained In:

Dissertation Abstracts International 56-03B.

System Details:

Mode of access: World Wide Web.

text file

Summary:

The underlying theme of the work presented in this thesis involves the use of the following three elements of superstructural control; (a) intermolecular interactions, (b) complementary shapes, and (c) transition metal liquid-based crystals to generate novel supermolecular assemblies. In chapters 2, 4, 5 and 6 I will demonstrate the use of design principles whereby intermolecular associations may be controlled by designing correlated molecular superstructures. Here, the presence of correlated structures is demonstrated through comparison of the structures, phase behavior and immiscibility studies between materials having the same phases but different structural shapes. Correlated smectic and columnar structures are shown which produce average rotations of 90$\sp\circ$ and 180$\sp\circ$ between nearest neighbors, where two or four molecules generate rod and disc-like shapes.

Additionally, I show that transition metal square pyramidal liquid crystalline complexes that contain metal-oxygen (M=O) bonds, chapters 3, 4, 5 and 6, have a propensity to exhibit weak and strong polymeric (-M=O-M=O-)$\sb{\rm n}$, interaction within their liquid crystalline phases and develop novel polar supermolecular assemblies. The degree and nature of these polymeric assemblies were elucidated using variable temperature infrared spectroscopy and x-ray spectroscopy where it is observed that complexes that form stronger polymers display a M=O stretching band at lower energy than the weaker polymeric phases. Furthermore it is shown that strong polymeric complexes exhibit relatively short (3.8A) correlations between the mesogens thereby allowing for strong intermolecular interactions while the weaker ones show much longer (4.6A) correlations.

Notes:

Thesis (Ph.D. in Chemistry) -- Graduate School of Arts and Sciences, University of Pennsylvania, 1994.

Source: Dissertation Abstracts International, Volume: 56-03, Section: B, page: 1413.

Supervisor: Timothy M. Swager.

Local Notes:

School code: 0175.

Access Restriction:

Restricted for use by site license.