Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman
This research focussed on the development of the synthetic methods and characterisation (structural, thermal, magnetic and redox properties) of two types of ionic copper(II) mixed-carboxylates: (a) Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4-a], and (b) [Cu2(p-H3NC6H4COO)a(CH3(CH2)14COO)4-a]Xa, where a =...
| _version_ | 1848772501831680000 |
|---|---|
| author | Zaimatul' Azian, Kamarazaman |
| author_facet | Zaimatul' Azian, Kamarazaman |
| author_sort | Zaimatul' Azian, Kamarazaman |
| building | UM Research Repository |
| collection | Online Access |
| description | This research focussed on the development of the synthetic methods and
characterisation (structural, thermal, magnetic and redox properties) of two types of
ionic copper(II) mixed-carboxylates: (a) Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4-a],
and (b) [Cu2(p-H3NC6H4COO)a(CH3(CH2)14COO)4-a]Xa, where a = 1, 2; n = 14, 10, 8,
and 6; X = Cl, CH3COO and CF3SO3. These complexes were designed to be thermally
stable and magnetic metallomesogens and/or metal-containing ionic liquids.
The synthetic methods used to prepare these complexes were one-pot reaction,
ligand-exchange reaction, and acid-carbonate-base reaction. A total of twelve (12)
complexes were successfully prepared and fully characterised (Table 1). The structural formulas of these complexes were deduced from elemental
analyses, FTIR and UV-vis spectroscopies. The thermal properties were determined by
TGA and DSC, while the mesomorphic properties were determined by OPM. The
magnetic properties were determined by Gouy method using a magnetic susceptibility
balance, and the redox properties by cyclic voltammetry. Additionally, GCMS was
used to analyze the products formed from the carbon-carbon bond-forming reaction of
methyl carbonyl (3,3-dimethyl-2-butanone).
The structure of most of the complexes were dimeric paddle-wheel with either
square planar or square pyramidal geometry at copper(II) centres.
Complex 1 had the highest thermal stability (Tdec = 424oC) compared to the other
complexes (Tdec = 200oC – 250oC). Additionally, the complexes with a higher ratio of
the alkylcarboxylate ligands (aromatic: aliphatic = 1:3) were more thermally stable; the
stability increases with increasing alkyl chain length. However, the opposite trend was
noted for the melting temperatures: complexes with a higher ratio of the
alkylcarboxylate ligands had a lower melting point.
Six of the complexes (Complex 2, Complexes 5 - 9) exhibited metallomesogenic
properties. However, the type of mesophase cannot be deduced with certainty from
OPM.
All complexes were magnetic at room-temperature. Except for Complex 1 which
showed a weak ferromagnetic interaction (μeff = 3.12 B.M.; 2J = 60 cm-1), the other
complexes had magnetism (μeff = 1.87 B.M. - 2.62 B.M.) which were lower than the
spin-only value for two unpaired electrons (μeff = 2.83 B.M.), with variable strength of
antiferromagnetic interaction (2J = -78 cm-1 to -346 cm-1). The complexes with a higher
ratio of the alkylcarboxylate ligands have a stronger antiferromagnetic interaction.
However, the difference in the chain length did not have much effect on the magnetic
interaction. |
| first_indexed | 2025-11-14T13:27:31Z |
| format | Thesis |
| id | um-3808 |
| institution | University Malaya |
| institution_category | Local University |
| last_indexed | 2025-11-14T13:27:31Z |
| publishDate | 2012 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | um-38082013-08-29T05:22:08Z Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman Zaimatul' Azian, Kamarazaman QD Chemistry This research focussed on the development of the synthetic methods and characterisation (structural, thermal, magnetic and redox properties) of two types of ionic copper(II) mixed-carboxylates: (a) Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4-a], and (b) [Cu2(p-H3NC6H4COO)a(CH3(CH2)14COO)4-a]Xa, where a = 1, 2; n = 14, 10, 8, and 6; X = Cl, CH3COO and CF3SO3. These complexes were designed to be thermally stable and magnetic metallomesogens and/or metal-containing ionic liquids. The synthetic methods used to prepare these complexes were one-pot reaction, ligand-exchange reaction, and acid-carbonate-base reaction. A total of twelve (12) complexes were successfully prepared and fully characterised (Table 1). The structural formulas of these complexes were deduced from elemental analyses, FTIR and UV-vis spectroscopies. The thermal properties were determined by TGA and DSC, while the mesomorphic properties were determined by OPM. The magnetic properties were determined by Gouy method using a magnetic susceptibility balance, and the redox properties by cyclic voltammetry. Additionally, GCMS was used to analyze the products formed from the carbon-carbon bond-forming reaction of methyl carbonyl (3,3-dimethyl-2-butanone). The structure of most of the complexes were dimeric paddle-wheel with either square planar or square pyramidal geometry at copper(II) centres. Complex 1 had the highest thermal stability (Tdec = 424oC) compared to the other complexes (Tdec = 200oC – 250oC). Additionally, the complexes with a higher ratio of the alkylcarboxylate ligands (aromatic: aliphatic = 1:3) were more thermally stable; the stability increases with increasing alkyl chain length. However, the opposite trend was noted for the melting temperatures: complexes with a higher ratio of the alkylcarboxylate ligands had a lower melting point. Six of the complexes (Complex 2, Complexes 5 - 9) exhibited metallomesogenic properties. However, the type of mesophase cannot be deduced with certainty from OPM. All complexes were magnetic at room-temperature. Except for Complex 1 which showed a weak ferromagnetic interaction (μeff = 3.12 B.M.; 2J = 60 cm-1), the other complexes had magnetism (μeff = 1.87 B.M. - 2.62 B.M.) which were lower than the spin-only value for two unpaired electrons (μeff = 2.83 B.M.), with variable strength of antiferromagnetic interaction (2J = -78 cm-1 to -346 cm-1). The complexes with a higher ratio of the alkylcarboxylate ligands have a stronger antiferromagnetic interaction. However, the difference in the chain length did not have much effect on the magnetic interaction. 2012 Thesis NonPeerReviewed application/pdf http://studentsrepo.um.edu.my/3808/1/1._Title_page%2C_abstract%2C_content.pdf application/pdf http://studentsrepo.um.edu.my/3808/2/CHAPTER_1.pdf application/pdf http://studentsrepo.um.edu.my/3808/3/CHAPTER_2.pdf application/pdf http://studentsrepo.um.edu.my/3808/4/CHAPTER_3.pdf application/pdf http://studentsrepo.um.edu.my/3808/5/CHAPTER_4.pdf application/pdf http://studentsrepo.um.edu.my/3808/6/CHAPTER_5.pdf application/pdf http://studentsrepo.um.edu.my/3808/7/Appendix.pdf http://pendeta.um.edu.my/client/default/search/results?qu=Synthesis+and+characterisation+of+thermally+stable+and+their+reactions+with+selected+ketones&te= Zaimatul' Azian, Kamarazaman (2012) Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman. Masters thesis, University of Malaya. http://studentsrepo.um.edu.my/3808/ |
| spellingShingle | QD Chemistry Zaimatul' Azian, Kamarazaman Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman |
| title | Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman |
| title_full | Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman |
| title_fullStr | Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman |
| title_full_unstemmed | Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman |
| title_short | Synthesis and characterisation of thermally stable Ka[Cu2(p-OC6H4COO)a(CH3(CH2)nCOO)4—a] and [Cu2(p-H3NC6H4COO)a(CH3(CH2)nCOO)4-a]Xa and their reactions with selected ketones / Zaimatul' Azian Kamarazaman |
| title_sort | synthesis and characterisation of thermally stable ka[cu2(p-oc6h4coo)a(ch3(ch2)ncoo)4—a] and [cu2(p-h3nc6h4coo)a(ch3(ch2)ncoo)4-a]xa and their reactions with selected ketones / zaimatul' azian kamarazaman |
| topic | QD Chemistry |
| url | http://pendeta.um.edu.my/client/default/search/results?qu=Synthesis+and+characterisation+of+thermally+stable+and+their+reactions+with+selected+ketones&te= http://pendeta.um.edu.my/client/default/search/results?qu=Synthesis+and+characterisation+of+thermally+stable+and+their+reactions+with+selected+ketones&te= http://studentsrepo.um.edu.my/3808/1/1._Title_page%2C_abstract%2C_content.pdf http://studentsrepo.um.edu.my/3808/2/CHAPTER_1.pdf http://studentsrepo.um.edu.my/3808/3/CHAPTER_2.pdf http://studentsrepo.um.edu.my/3808/4/CHAPTER_3.pdf http://studentsrepo.um.edu.my/3808/5/CHAPTER_4.pdf http://studentsrepo.um.edu.my/3808/6/CHAPTER_5.pdf http://studentsrepo.um.edu.my/3808/7/Appendix.pdf |