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Synthesis and photochemical characterisation of luminescent gold complexes for technological applications. / Jeremie Guillaume Pichereau

Swansea University Author: Jeremie Guillaume Pichereau

Abstract

Two new precursors of dithiolate ligands, 2,6-dimercaptopyrazine (DMPA) and 2,6-dimercaptonicotinic acid (ADMN) have been synthesised and characterised. Their photochemical properties have been studied along with those of other known N-heterocyclic thiol compounds namely: (4,6-dimercaptopyrimidine (...

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Published: 2008
Institution: Swansea University
Degree level: Doctoral
Degree name: Ph.D
URI: https://cronfa.swan.ac.uk/Record/cronfa42464
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spelling 2018-08-02T16:24:29.3377956 v2 42464 2018-08-02 Synthesis and photochemical characterisation of luminescent gold complexes for technological applications. d196db1d418795f8d5cba99a49a55bf5 NULL Jeremie Guillaume Pichereau Jeremie Guillaume Pichereau true true 2018-08-02 Two new precursors of dithiolate ligands, 2,6-dimercaptopyrazine (DMPA) and 2,6-dimercaptonicotinic acid (ADMN) have been synthesised and characterised. Their photochemical properties have been studied along with those of other known N-heterocyclic thiol compounds namely: (4,6-dimercaptopyrimidine (46PYRI), 2,4-dimercaptopyrimidine (24PYRI), 5,6-diamino-2,4-dimercaptopyrimidine (NPYRI) and 2,6-dimercaptopyridine (DMP)). All these compounds can be in a tautomeric equilibrium between thiol and thione forms, and it has been shown that in polar media the thioketone is the dominant species. All emit in a glass at 77 K and room temperature, but only 24PYR1 and 46PYRI give phosphorescence at 77 K (T = 380 mus and 57 mus respectively). The presence of a thiol group effectively quenches the phosphorescence and only fluorescence is observed for the other compounds. They all have an irreversible electrochemistry. The crystal structure of 46PYRI is reported for the first time. Twenty-five new binuclear gold(I) phosphine derivatives of these dithiolate ligands have been synthesised: i.e. with bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane and bis(diphenylphosphino)butane, for annular complexes, or with triphenylphosphine for open ring compounds. A mononuclear triphenylphosphinegold(I) complex with DMP is also reported. Gold-gold interactions were absent from the two crystal structures obtained. All these compounds show phosphorescence in the solid state at RT and in a glass at 77 K, but only complexes with DMP as dithiolate emit in solution at RT (through phosphorescence also). The origin of the luminescence is thought to be from a mixture of LMCT or ILCT excited states. Complexes with electron-withdrawing groups (e.g. ADMN) on the thiolate promote the ILCT excited state whereas electron-donating groups (e.g. NPYRI) promote the LMCT excited state. All complexes studied gave irreversible electrochemistry. Ab initio studies on the dithiols confirm the greater stability of the thioketone form in polar solvents. Structural simulations of the binuclear gold(I) complexes confirm both the absence of an aurophilic interaction and the origin of luminescence. E-Thesis Inorganic chemistry. 31 12 2008 2008-12-31 COLLEGE NANME Chemistry COLLEGE CODE Swansea University Doctoral Ph.D 2018-08-02T16:24:29.3377956 2018-08-02T16:24:29.3377956 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Jeremie Guillaume Pichereau NULL 1 0042464-02082018162456.pdf 10798172.pdf 2018-08-02T16:24:56.5600000 Output 16650750 application/pdf E-Thesis true 2018-08-02T16:24:56.5600000 false
title Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
spellingShingle Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
Jeremie Guillaume Pichereau
title_short Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
title_full Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
title_fullStr Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
title_full_unstemmed Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
title_sort Synthesis and photochemical characterisation of luminescent gold complexes for technological applications.
author_id_str_mv d196db1d418795f8d5cba99a49a55bf5
author_id_fullname_str_mv d196db1d418795f8d5cba99a49a55bf5_***_Jeremie Guillaume Pichereau
author Jeremie Guillaume Pichereau
author2 Jeremie Guillaume Pichereau
format E-Thesis
publishDate 2008
institution Swansea University
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description Two new precursors of dithiolate ligands, 2,6-dimercaptopyrazine (DMPA) and 2,6-dimercaptonicotinic acid (ADMN) have been synthesised and characterised. Their photochemical properties have been studied along with those of other known N-heterocyclic thiol compounds namely: (4,6-dimercaptopyrimidine (46PYRI), 2,4-dimercaptopyrimidine (24PYRI), 5,6-diamino-2,4-dimercaptopyrimidine (NPYRI) and 2,6-dimercaptopyridine (DMP)). All these compounds can be in a tautomeric equilibrium between thiol and thione forms, and it has been shown that in polar media the thioketone is the dominant species. All emit in a glass at 77 K and room temperature, but only 24PYR1 and 46PYRI give phosphorescence at 77 K (T = 380 mus and 57 mus respectively). The presence of a thiol group effectively quenches the phosphorescence and only fluorescence is observed for the other compounds. They all have an irreversible electrochemistry. The crystal structure of 46PYRI is reported for the first time. Twenty-five new binuclear gold(I) phosphine derivatives of these dithiolate ligands have been synthesised: i.e. with bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane and bis(diphenylphosphino)butane, for annular complexes, or with triphenylphosphine for open ring compounds. A mononuclear triphenylphosphinegold(I) complex with DMP is also reported. Gold-gold interactions were absent from the two crystal structures obtained. All these compounds show phosphorescence in the solid state at RT and in a glass at 77 K, but only complexes with DMP as dithiolate emit in solution at RT (through phosphorescence also). The origin of the luminescence is thought to be from a mixture of LMCT or ILCT excited states. Complexes with electron-withdrawing groups (e.g. ADMN) on the thiolate promote the ILCT excited state whereas electron-donating groups (e.g. NPYRI) promote the LMCT excited state. All complexes studied gave irreversible electrochemistry. Ab initio studies on the dithiols confirm the greater stability of the thioketone form in polar solvents. Structural simulations of the binuclear gold(I) complexes confirm both the absence of an aurophilic interaction and the origin of luminescence.
published_date 2008-12-31T03:53:01Z
_version_ 1763752627477151744
score 11.012678

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