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Guest binding, redox, and molecular ...

Tiedemann, Bryan Erik.

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Guest binding, redox, and molecular transport properties of supramolecular coordination assemblies.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Guest binding, redox, and molecular transport properties of supramolecular coordination assemblies./
Author:	Tiedemann, Bryan Erik.
Description:	189 p.
Notes:	Adviser: Kenneth N. Raymond.
Contained By:	Dissertation Abstracts International68-08B.
Subject:	Chemistry, Analytical. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3275626
ISBN:	9780549172161

Guest binding, redox, and molecular transport properties of supramolecular coordination assemblies.
Tiedemann, Bryan Erik.

Guest binding, redox, and molecular transport properties of supramolecular coordination assemblies. - 189 p.

Adviser: Kenneth N. Raymond.

Thesis (Ph.D.)--University of California, Berkeley, 2007.

The rich host-guest chemistry of the M4L6 tetrahedral cluster developed by Raymond and coworkers has been studied for the last ten years, yet this dissertation will argue that its full capabilities have yet to be realized. Several different physical techniques have been used to explore the properties of the M4L6 supramolecular cluster, providing a different perspective. A brief summary of the known properties of M 4L6 is given in Chapter 1, as well a description of how electrochemical techniques can apply to supramolecular systems.

ISBN: 9780549172161Subjects--Topical Terms:

586156
Chemistry, Analytical.

Guest binding, redox, and molecular transport properties of supramolecular coordination assemblies.
LDR:03478nam 2200325 a 45 001 946088
005 20110523
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020 $a 9780549172161
035 $a (UMI)AAI3275626
035 $a AAI3275626
040 $a UMI $c UMI
100 1 $a Tiedemann, Bryan Erik. $3 1269498
245 1 0 $a Guest binding, redox, and molecular transport properties of supramolecular coordination assemblies.
300 $a 189 p.
500 $a Adviser: Kenneth N. Raymond.
500 $a Source: Dissertation Abstracts International, Volume: 68-08, Section: B, page: 5232.
502 $a Thesis (Ph.D.)--University of California, Berkeley, 2007.
520 $a The rich host-guest chemistry of the M4L6 tetrahedral cluster developed by Raymond and coworkers has been studied for the last ten years, yet this dissertation will argue that its full capabilities have yet to be realized. Several different physical techniques have been used to explore the properties of the M4L6 supramolecular cluster, providing a different perspective. A brief summary of the known properties of M 4L6 is given in Chapter 1, as well a description of how electrochemical techniques can apply to supramolecular systems.
520 $a Chapter 2 is concerned with molecular transport, using diffusion NMR methods to measure diffusion coefficients. Exterior binding of alkylammonium cations was clearly observed from changes in the diffusion coefficient, confirming that strong ion pairing interactions persist in aqueous solution. The effect of different alkali cations on the diffusion rate is also discussed.
520 $a The thermodynamics of host-guest interactions are investigated in Chapter 3 using isothermal titration calorimetry to directly measure reaction heats. Large heats are observed when [Ga4L6]12- is titrated with R4N+ in aqueous solution (R = Me, Et, Pr), and the resulting thermodynamic parameters for the overall processes are reported.
520 $a A novel partial guest encapsulation mode is described in Chapter 4. Cationic ruthenium sandwich complexes with pendant linear chains are encapsulated by [Ga4L6]12- with the result that part of the long chains protruding out of the host to the exterior. Chains terminated by an anionic group are permanently extruded through the three-fold symmetric aperture in a triangular face of the host, confirming the non-dissociative guest exchange mechanism described by Davis et al. The methyl terminus of neutral chains can reside either inside or outside the cluster, and such a chain with six carbons rapidly extends and retracts at room temperature, moving the methyl group in and out of the host cavity. This fluxional structure exemplifies the dynamic second-order Jahn-Teller effect.
520 $a Chapters 5 and 6 describe electrochemical experiments with M4L 6. Chapter 5 explores whether redox-active cations can be reduced while encapsulated within a redox-silent host; the answer is no for the systems examined. Chapter 6 investigates redox-active vanadium complexes, including the [V4L6]8-cluster with a redox-silent Et4N+ guest. The results demonstrate that, while the vertices are redox-active in the M4L6 cluster, there is no interaction between them.
590 $a School code: 0028.
650 4 $a Chemistry, Analytical. $3 586156
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0486
690 $a 0488
710 2 $a University of California, Berkeley. $3 687832
773 0 $t Dissertation Abstracts International $g 68-08B.
790 $a 0028
790 1 0 $a Raymond, Kenneth N., $e advisor
791 $a Ph.D.
792 $a 2007
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3275626