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Nanyang Technological University

1. Ng, Yik Yie. Development of earth-abundant copper photosensitizers for artificial photosynthesis .

Degree: 2019, Nanyang Technological University

A series of bis(arylimino)acenaphthene (Ar-BIAN) CuI complexes have been synthesized in three or fewer steps. A comprehensive study of their electrochemical and spectroscopic properties has been performed. The Ar-BIAN CuI complexes herein have been incorporated into dye-sensitized solar cells (DSSCs) or photoredox reaction to investigate their potential applications. In Chapter 2, two new Ar-BIAN ligands and their corresponding homoleptic CuI complexes were synthesized and studied. The solution and solid-state absorption characteristics of the complexes have been examined. They were found to be panchromatic and absorb into the near-infrared (NIR) region. Notably, the crystal structure of one of the complexes gave an unprecedented rhombically distorted square planar geometry about the metal center. Computational studies revealed the non-covalent interactions between the aromatic functionalities and among the iodide atoms. To investigate the practical application of the complexes, they were anchored onto a metal oxide surface and incorporated into dye-sensitized solar cells (DSSCs). However, the efficiencies obtained and discussed in Chapter 3 were lower than expectations. In Chapter 4, another group of panchromatic Ar-BIAN CuI complexes were synthesized and characterized. Electrochemical measurements showed that two of the complexes can be regenerated after redox activities. From the photoluminescence experiments, one of the complexes displayed a weakly emissive signal. According to the time-correlated single-photon counting (TCSPC) measurements, the photoluminescence has a bi-exponential lifetime (τ1 = 3.6 ns; τ2 = 11 ns). Following on, the luminescent complex was employed in the photocatalysis of atom transfer radical addition (ATRA) reactions. Spectroelectrochemical studies were carried out to obtain the UV-visible absorption spectra of the CuII species formed upon oxidation. A comparison of the absorption spectra of the independently synthesized CuII complex and the species formed during the photoredox reaction led us to conclude that the intermediate contained CBr3 or Br- attached to the CuII metal center.

Subjects/Keywords: DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds; DRNTU::Science::Chemistry::Physical chemistry::Photochemistry

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APA (6th Edition):

Ng, Y. Y. (2019). Development of earth-abundant copper photosensitizers for artificial photosynthesis . (Thesis). Nanyang Technological University. Retrieved from http://hdl.handle.net/10220/47719

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16th Edition):

Ng, Yik Yie. “Development of earth-abundant copper photosensitizers for artificial photosynthesis .” 2019. Thesis, Nanyang Technological University. Accessed March 20, 2019. http://hdl.handle.net/10220/47719.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7th Edition):

Ng, Yik Yie. “Development of earth-abundant copper photosensitizers for artificial photosynthesis .” 2019. Web. 20 Mar 2019.

Vancouver:

Ng YY. Development of earth-abundant copper photosensitizers for artificial photosynthesis . [Internet] [Thesis]. Nanyang Technological University; 2019. [cited 2019 Mar 20]. Available from: http://hdl.handle.net/10220/47719.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Ng YY. Development of earth-abundant copper photosensitizers for artificial photosynthesis . [Thesis]. Nanyang Technological University; 2019. Available from: http://hdl.handle.net/10220/47719

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

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