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Electron-Transfer in Covalently Coupled Donor-Acceptor Complexes


Bachrach, Max (1996) Electron-Transfer in Covalently Coupled Donor-Acceptor Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/tzkw-0q94.


A picosecond transient absorption experiment has been constructed and used for the study of intramolecular electron-transfer (ET) in three molecular systems. The first of these is a donor-bridge-acceptor (D(br)A) complex composed of a d⁸-d⁸ iridium core covalently coupled to two pyridinium acceptors with flexible phosphonite spacers. Varying the pyridiniums' substituents allows control of the driving-forces (ΔG°) of the photoinduced ET reactions from the core's singlet and triplet states. The rates of these reactions have been determined from steady-state and time-resolved emission experiments. Picosecond transient absorption has been used to measure the rates of subsequent charge-recombination, and determine their dependencies on ΔG°. The reorganization energy accompanying intramolecular electron-transfer within this system (λ ≈ 0.86 eV) has been determined by fitting the rates of photoinduced and thermal reactions to a single-mode quantum-mechanical ET model.

The rates of all the photoinduced and thermal ET reactions have been measured as a function of temperature (200° K - 280° K). These data show that the charge-recombination reactions, which lie within the Marcus inverted region (ΔG° > λ), have rates (kBET) that are strongly dependent on temperature. Deuteration of the pyridinium acceptor has a temperature independent effect (kH/kD = 1.2) on kBET, indicating that, although the inverted region reactions within these complexes exhibit behavior that is remarkably classical, quantum-mechanical effects do need to be considered. Both temperature and isotope effects suggest that the molecules' low internal reorganization energies (λin = 0.006 eV) account for their ET behavior.

Less comprehensive studies of two other electron-transfer systems are also reported. Unlike the iridium system, in which the donor-acceptor electronic coupling HAB is less than 100 cm-1, the couplings within these are over 2000 cm-1. It has been found that despite the large amount of coupling between the metals of [(bpy)(tpy)RuIICNRuII(NH3)5]2+ (bpy = 2,2'-bipyridine; tpy = 2,2',2"-terpyridine), our transient absorption experiment is able to detect formation of a charge-separated state following excitation into the Ru → immine charge-transfer band. It is proposed that this species can be described as [(bpy)(tpy•-)RuIICNRuIII(NH3)5]2+ and that unusually low coupling between the tpy ligand and the oxidized ruthenium leads to slow (1 x 1010 s-1) charge-recombination.

The ground-state absorption features and excited-state decay kinetics of a series of ferrocene-based D(br)A complexes have also been measured. It is proposed that HAB is much larger than 2000 cm-1 for these complexes, and plays an important role in determining their nonlinear optical properties.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Gray, Harry B.
Thesis Committee:
  • Lewis, Nathan S. (chair)
  • Gray, Harry B.
  • Grubbs, Robert H.
  • Okumura, Mitchio
Defense Date:21 July 1995
Record Number:CaltechTHESIS:12152020-011716999
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:14028
Deposited By: Mel Ray
Deposited On:15 Dec 2020 02:04
Last Modified:17 Dec 2020 23:28

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