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Spectroscopy and photochemistry of polynuclear metal complexes


Maverick, Andrew William (1982) Spectroscopy and photochemistry of polynuclear metal complexes. Dissertation (Ph.D.), California Institute of Technology.


NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. The photochemical and spectroscopic properties of two classes of polynuclear metal complexes have been studied. Molybdenum and Tungsten Cluster Halides: The cubic ions [...], [...], and [...] are luminescent, with lifetimes approaching 200 [...] in solution at room temperature. The luminescent excited state of [...] is probably associated with a transition localized on the central Mo6 core. Both this excited state and the corresponding ground state undergo facile one electron oxidation. These features make the cluster ions attractive for experiments in photochemical energy storage. Also discussed is evidence from magnetic and spectroscopic studies bearing on the electronic structures of the cluster ions. Rhodium Isocyanide Complexes: Various thermal and photochemical reactions in the system [...] (b = 1,3-diisocyanopropane) have been examined. The possibility of photocatalytic hydrogen production sensitized by [...] and [...], previously shown to produce [...] stoichiometrically on irradiation in strongly acidic solution, was explored. Experiments were also conducted with [...] (TMB = 2,5-diisocyano-2,5-dimethylhexane) in the hopes of accomplishing similar energy storage reactions. The equilibria in acidic aqueous solution involving these species as well as oligomers of intermediate oxidation state were also studied. Kinetic studies of the reduction of [...] by [...] and of thermal and photochemical oxidation of [...] by [...] were inconclusive.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:bromide; chloride; cluster; isocyanide; luminescence; molybdenum; photoredox; rhodium; tungsten
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:The Herbert Newby McCoy Award, 1981
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Gray, Harry B.
Thesis Committee:
  • Gray, Harry B. (chair)
  • Bercaw, John E.
  • Marsh, Richard Edward
  • Goddard, William A., III
Defense Date:4 September 1981
Non-Caltech Author Email:maverick (AT)
Record Number:CaltechETD:etd-03092005-130854
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:905
Deposited By: Imported from ETD-db
Deposited On:09 Mar 2005
Last Modified:26 Dec 2012 02:33

Thesis Files

PDF (Maverick_aw_1982.pdf) - Final Version
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