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SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES

Eryazici, Ibrahim

Abstract Details

2007, Doctor of Philosophy, University of Akron, Polymer Science.
Highly ordered, regularly repeating molecular architectures, constructed via self-assembly techniques, have gained importance over the last three decades due to their potential utilitarian applications. A key construction strategy has relied on the synthesis of specific building blocks capable of forming “higher-ordered” stable structures that have useful properties that can be used as molecular and supramolecular devices. To this end, mono and bis(terpyridine) ligands have been widely used because of their well known photochemical and electronic properties, as well as their ability to facilitate directed, metal-mediated self-assembly. However, limited accessibility to unsymmetrically functionalized terpyridines has restricted their potential use in the construction of more complex infrastructures. For this purpose, methyl-, methoxy-carbonyl- and cyano-substitution patterns on the 4,4''-positions of 4'-arylterpyridine were chosen since these functionalities afforded simple routes to a variety of useful substituted building blocks for higher-ordered supramacromolecular architectures. Single crystal X-ray studies of these terpyridines revealed that molecules of the diester terpyridine (approximately coplanar) are stacked by the overlap of the central pyridine rings in consecutive layers with mean interplanar distances of 3.4 Å (π – π interactions) in the solid state. Moreover, functionalized bis(terpyridine) ligands were achieved via the Kröhnke method and Pd(0) coupling strategy using either 1,3-toluenylbisboronic acid or 1,3-diethynyltoluene with meta- or para-I or Br-phenylterpyridines. A dinuclear tetracationic Fe(II) complex was prepared via metal-directed self-assembly. The chair-like molecular architecture was primarily characterized by X-ray crystallography, mass spectroscopy (ESI-MS), as well as 1H NMR, UV-vis, and CV experiments. Crystal packing of this metallomacrocycle revealed that it formed channels that encapsulated water and MeCN. The low temperature 1H NMR studies suggested that tpy-Fe-tpy moieties in the dimer were interlocked and resembled a spur gear relationship. Surprisingly, dinuclear and trinuclear metallomacrocycles were formed when 1,3-bis(2,2';6',2''-terpyridine-4'-phen-3-ylethynyl)toluene was treated with equimolar amount of Ru(II) that was confirmed by MALDI-TOF mass and NMR spectroscopy. The construction of a heteronuclear (Ru4Fe2) hexameric metallomacrocycle with methyl- and carbonyl-functionalized bis(terpyridyl) moieties was achieved by Pd(0) coupling strategy for potential solar cell applications and supramolecular aggregation of the resulting hexamers through H-bonding. Carboxylic acid functionalized mono- and dinuclear homo- and heteroleptic Ru(II) precursors were also prepared for the same purposes. The single crystal X-ray structure of a homoleptic Ru(II) complex with tetra-ethoxycarbonyl and di(iodo) groups revealed short iodo-carbonyl interactions.
George Newkome (Advisor)
309 p.

Recommended Citations

Citations

  • Eryazici, I. (2007). SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1195677178

    APA Style (7th edition)

  • Eryazici, Ibrahim. SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES. 2007. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1195677178.

    MLA Style (8th edition)

  • Eryazici, Ibrahim. "SUPRAMOLECULAR CHEMISTRY OF FUNCTIONALIZED TERPYRIDINES." Doctoral dissertation, University of Akron, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=akron1195677178

    Chicago Manual of Style (17th edition)