Cyclometalated Platinum β-Diketiminate Complexes

A series of cyclometalated platinum complexes with ancillary β-diketiminate (NacNac) ligands, prepared by a general synthetic route are described. Two different cyclometalating (C^N) ligands―2-phenylpyridine (ppy) and 2-(2,4-difluorophenyl)pyridine (F2ppy)―are used in concert with two different fluorinated NacNac ligands (NacNacF6 and NacNacF18) ‒ to furnish a suite of complexes. The complexes were prepared by metathesis reactions of chloro-bridged dimers [Pt(C^N)(μ-Cl)]2 with lithium salts of the ancillary (LX) ligand. Two structure types can be accessed, depending on the reaction temperature. At lower temperature (ca. 80 °C) bimetallic structures with a bridging NacNac and bridging chloride were prepared, and when the temperature was increased (ca. 100 °C) monometallic Pt(C^N)2(NacNac) complexes formed. The complexes were characterized by X-ray crystallography, and were subjected to in-depth optical and electrochemical interrogation. Fluorination of these ligands by introducing CF3 substituents onto the ligand backbone and/or the N-aryl substituents lead to pronounced changes in the redox properties. All the complexes show a reversible redox couple that was sensitive to the degree of fluorination on the ancillary ligand. Introduction of CF3 groups at the 3- and 5- positions of the N-aryl substituents shifted the potential positive by ca. 50 – 110 mV, but the same substitution minimally perturbed the UV-Vis absorption spectra of the complexes.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

Masters

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Houston

Year dc:date.issued

2017

Author dc:creator

• Islam, Mohammad Din 1986-

Advisor dc:contributor.advisor

• Teets, Thomas S.

Committee members dc:contributor.committeemember

• Halasyamani, P. Shiv
• Van Caemelbecke, Eric
• Do, Loi H.
• Brgoch, Jakoah

• Cyclometalated
• Β-diketiminate

Statement dc:rights

• The author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/10657/14953

OAI identifier oai:identifier

oai:uh-ir.tdl.org:10657/14953