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Masters_Thesis_Christopher_Ziehm.pdf (1.98 MB)

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ENHANCEMENT OF ELECTRONIC COUPLING IN METAL-METAL QUADRUPLY BONDED COMPLEXES

Ziehm, Christopher Joseph
http://rave.ohiolink.edu/etdc/view?acc_num=osu1416315259

Abstract Details

2014, Master of Science, Ohio State University, Chemistry.
The study of electronic communication in a variety of inorganic systems has been evident in the understanding of fundamental electron transfer. These mixed valence system follow one of two main motifs. The mixed valence system [M-B-M]+ describes two metal redox centers connected by an organic bridge which facilitates electronic coupling to the redox centers. The [L-M-L]- system corresponds to two organic ligand redox centers that are connected by a metal center which facilitates the electronic coupling. Dimetal quadruply bonded complexes, which include dimolybdenum or ditungsten metal centers, are a unique class of inorganic molecules that through synthetic modification can adapt either one of these two forms. The complexes in this study have been synthesized and characterized and are of the form M2(TiPB)2(L)2 where TiPB = 2,4,6-triisopropylbenzoate, L = 4-[2-(4-pyridinyl)ethenyl]-benzoate, and M = Mo (I) or W (II). In addition, the tris(pentafluorophenyl)boron adducts of the afore mentioned complexes have been studied, IB and IIB respectively. Upon reduction to radical anions IB- and IIB-, the relative enhancement in electronic coupling of these systems was investigated. Electronic structure calculations, UV-Vis-NIR spectroscopy, electrochemical measurements, and various characterization techniques were utilized. The splitting in the reduction potentials, ΔE1/2, of IB and IIB is a clear indication of the degree of coupling in these [L-M-L]- systems, showing that the tungsten metal centers are more effective at coupling the two redox centers. The appearance and shape of a new low energy IVCT absorption band in the NIR upon reduction aid in the Class III fully delocalized mixed valence ion assignment for both complexes IB and IIB. The enhancement of electronic communication between two ligand based redox centers by a dimetal center was investigated in this study by incorporation of an extended organic ligand ∏ system capped with the sterically protecting boron moieties to increase the extent of electronic communication between the two ligand-based redox centers. The relative change in electronic coupling was compared to other bis-bis analogs to see the overall effect.
Malcolm Chisholm, Dr. (Advisor)
James Cowan, Dr. (Committee Member)
84 p.
Chemistry

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Citations

  • Ziehm, C. J. (2014). ENHANCEMENT OF ELECTRONIC COUPLING IN METAL-METAL QUADRUPLY BONDED COMPLEXES [Master's thesis, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1416315259

    APA Style (7th edition)

  • Ziehm, Christopher. ENHANCEMENT OF ELECTRONIC COUPLING IN METAL-METAL QUADRUPLY BONDED COMPLEXES. 2014. Ohio State University, Master's thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1416315259.

    MLA Style (8th edition)

  • Ziehm, Christopher. "ENHANCEMENT OF ELECTRONIC COUPLING IN METAL-METAL QUADRUPLY BONDED COMPLEXES." Master's thesis, Ohio State University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=osu1416315259

    Chicago Manual of Style (17th edition)

osu1416315259
409
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