Skip to Main Content
 

Global Search Box

 
 
 
 

ETD Abstract Container

Abstract Header

Terpyridine-Based Metallo-Supramolecular Architectures: From Structure to Function

Elbatal, Hany

Abstract Details

2013, Doctor of Philosophy, University of Akron, Polymer Science.
The research and applications of functional materials continue to grow rapidly in order to match the materials and energy needs of an increasing population. In this regard, perylene is a stable, organic material that possesses a rich chemistry and unique chemical, physical, and electronic properties. The molecular organization into predesigned geometries such as: cages, dendrimers, macrocycles and polymers, can add a profound enhancement to the material functional characteristics. At the heart of metallosupramolecular chemistry, tpy-M-tpy binding is a pivotal tool to construct complex and functional architectures. This dissertation reviews the chemical, structural, physical, and electrochemical properties of perylene with an emphasize on its metallosupramolecular chemistry. The synthesis of perylene-containing bis-, tetrakis-, and hexakis-terpyridine ligands along with their corresponding heteroleptic tpyRuIItpy complexes was achieved. These high molecular weight nano-dendritic architectures were characterized using 1H NMR, 13C NMR, COSY, and ESI-MS. These complexes exhibit broad absorption spectra (250-625 nm) and high molar absorption coefficients that are proportional to the number of photoactive units. The synthesis of supramolecular dyes based on tpy-RuII-tpy motifs connected to perylene-core either in bay- or peri-positions was demonastrated. The structures of these materials were confirmed using a combination of 1H NMR, 13C NMR, COSY, ESI-MS, and their electrochemical properties were studied via Cyclic Voltametry. These dyes were utilized as active ingredients for DSSCs, of which the photovoltaic properties were described. Fluorescent cyclic metallosupramolecular architectures were obtained via tpyZnIItpy mediated self-assembly of two aminobisterpyridine containing perylene ligands that were synthesized in a multistep procedure, the chemical structure and purity of both ligands and complexes were assured using a combination of 1H NMR, 13C NMR, COSY, and ESI-MS. DOSY was utilized to investigate the dimensions of the metallocycles that were compared to the values obtained from the energy minimized molecular modeling. The photophysical properties of these macrocycles showed strong fluorescence suggesting their potential use in LED. The formation of novel cyclic complexes including trimer and heteroleptic tetramers was achieved. The UV-Vis absorption and emission spectra of these materials were studied, and their chemical structures were illucidated via a combination of spectroscopic techniques including 1H NMR, ESI-MS, and MALDI-TOF-MS. Molecular modeling simulation of these nanosized complexes revealed cavities that can be used for host-guest chemistry.
George Newkome, Dr. (Advisor)
Steven Cheng, Dr. (Committee Member)
Chrys Wesdemiotis, Dr. (Committee Member)
Matthew Becker, Dr. (Committee Member)
Alamgir Karim, Dr. (Committee Member)
213 p.

Recommended Citations

Citations

  • Elbatal, H. (2013). Terpyridine-Based Metallo-Supramolecular Architectures: From Structure to Function [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1384367887

    APA Style (7th edition)

  • Elbatal, Hany. Terpyridine-Based Metallo-Supramolecular Architectures: From Structure to Function . 2013. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1384367887.

    MLA Style (8th edition)

  • Elbatal, Hany. "Terpyridine-Based Metallo-Supramolecular Architectures: From Structure to Function ." Doctoral dissertation, University of Akron, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=akron1384367887

    Chicago Manual of Style (17th edition)