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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. doi:10.7907/PBEA-8W62.


The photochemical and spectroscopic properties of two classes of polynuclear metal complexes have been studied.

Molybdenum and Tungsten Cluster Halides: The cubic ions Mo6Cl142-, Mo6Br142-, and W6Cl142- are luminescent, with lifetimes approaching 200 μs in solution at room temperature. The luminescent excited state of Mo6Cl142- 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 Rh2b42+ - Rh4b86+ - Rh2b44+ (b = 1,3-diisocyanopropane) have been examined. The possibility of photocatalytic hydrogen production sensitized by Rh2b42+ and Rh4b86+, previously shown to produce H2 stoichiometrically on irradiation in strongly acidic solution, was explored. Experiments were also conducted with Rh2(TMB)42+ (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 Rh2b44+ by H2 and of thermal and photochemical oxidation of Rh4b86+ by O2 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):
  • Bercaw, John E.
Thesis Committee:
  • Gray, Harry B. (chair)
  • Marsh, Richard Edward
  • Dougherty, Dennis A.
  • Bercaw, John E.
  • Goddard, William A., III
Defense Date:4 September 1981
Non-Caltech Author Email:maverick (AT)
Funding AgencyGrant Number
Standard Oil CompanyUNSPECIFIED
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:18 Jun 2020 19:24

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