The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes
A 1,4,7,10-tetraazacyclododecane (cyclen) variant bearing two thiosemicarbazone pendant groups has been prepared. The ligand forms complexes with Mn<sup>2+</sup>, Co<sup>2+</sup> and Zn<sup>2+</sup>. X-ray crystallography of the Mn<sup>2+</sup>, Co<...
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MDPI AG
2021-06-01
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| Series: | Molecules |
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| author | Melyssa L. Grieve Patrick R. W. J. Davey Craig M. Forsyth Brett M. Paterson |
| author_facet | Melyssa L. Grieve Patrick R. W. J. Davey Craig M. Forsyth Brett M. Paterson |
| author_sort | Melyssa L. Grieve |
| collection | DOAJ |
| description | A 1,4,7,10-tetraazacyclododecane (cyclen) variant bearing two thiosemicarbazone pendant groups has been prepared. The ligand forms complexes with Mn<sup>2+</sup>, Co<sup>2+</sup> and Zn<sup>2+</sup>. X-ray crystallography of the Mn<sup>2+</sup>, Co<sup>2+</sup> and Zn<sup>2+</sup> complexes showed that the ligand provides a six-coordinate environment for the metal ions. The Mn<sup>2+</sup> and Zn<sup>2+</sup> complexes exist in the solid state as racemic mixtures of the Δ(δ,δ,δ,δ)/Λ(λ,λ,λ,λ) and Δ(λ,λ,λ,λ)/Λ(δ,δ,δ,δ) diastereomers, and the Co<sup>2+</sup> complex exists as the Δ(δ,δ,δ,δ)/Λ(λ,λ,λ,λ) and Δ(λ,λ,λ,δ)/Λ(δ,δ,δ,λ) diastereomers. Density functional theory calculations indicated that the relative energies of the diastereomers are within 10 kJ mol<sup>−1</sup>. Magnetic susceptibility of the complexes indicated that both the Mn<sup>2+</sup> and Co<sup>2+</sup> ions are high spin. The ligand was radiolabelled with gallium-68, in the interest of developing new positron emission tomography imaging agents, which produced a single species in high radiochemical purity (>95%) at 90 °C for 10 min. |
| first_indexed | 2024-03-10T10:24:47Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T10:24:47Z |
| publishDate | 2021-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-c336d4fe181e45dab623a9c0af75594d2023-11-22T00:10:19ZengMDPI AGMolecules1420-30492021-06-012612364610.3390/molecules26123646The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) ComplexesMelyssa L. Grieve0Patrick R. W. J. Davey1Craig M. Forsyth2Brett M. Paterson3School of Chemistry, Monash University, Clayton, VIC 3800, AustraliaSchool of Chemistry, Monash University, Clayton, VIC 3800, AustraliaSchool of Chemistry, Monash University, Clayton, VIC 3800, AustraliaSchool of Chemistry, Monash University, Clayton, VIC 3800, AustraliaA 1,4,7,10-tetraazacyclododecane (cyclen) variant bearing two thiosemicarbazone pendant groups has been prepared. The ligand forms complexes with Mn<sup>2+</sup>, Co<sup>2+</sup> and Zn<sup>2+</sup>. X-ray crystallography of the Mn<sup>2+</sup>, Co<sup>2+</sup> and Zn<sup>2+</sup> complexes showed that the ligand provides a six-coordinate environment for the metal ions. The Mn<sup>2+</sup> and Zn<sup>2+</sup> complexes exist in the solid state as racemic mixtures of the Δ(δ,δ,δ,δ)/Λ(λ,λ,λ,λ) and Δ(λ,λ,λ,λ)/Λ(δ,δ,δ,δ) diastereomers, and the Co<sup>2+</sup> complex exists as the Δ(δ,δ,δ,δ)/Λ(λ,λ,λ,λ) and Δ(λ,λ,λ,δ)/Λ(δ,δ,δ,λ) diastereomers. Density functional theory calculations indicated that the relative energies of the diastereomers are within 10 kJ mol<sup>−1</sup>. Magnetic susceptibility of the complexes indicated that both the Mn<sup>2+</sup> and Co<sup>2+</sup> ions are high spin. The ligand was radiolabelled with gallium-68, in the interest of developing new positron emission tomography imaging agents, which produced a single species in high radiochemical purity (>95%) at 90 °C for 10 min.https://www.mdpi.com/1420-3049/26/12/3646thiosemicarbazonemacrocycletransition metalcyclengallium-68coordination chemistry |
| spellingShingle | Melyssa L. Grieve Patrick R. W. J. Davey Craig M. Forsyth Brett M. Paterson The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes Molecules thiosemicarbazone macrocycle transition metal cyclen gallium-68 coordination chemistry |
| title | The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes |
| title_full | The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes |
| title_fullStr | The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes |
| title_full_unstemmed | The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes |
| title_short | The Synthesis of a Bis(thiosemicarbazone) Macrocyclic Ligand and the Mn(II), Co(II), Zn(II) and <sup>68</sup>Ga(III) Complexes |
| title_sort | synthesis of a bis thiosemicarbazone macrocyclic ligand and the mn ii co ii zn ii and sup 68 sup ga iii complexes |
| topic | thiosemicarbazone macrocycle transition metal cyclen gallium-68 coordination chemistry |
| url | https://www.mdpi.com/1420-3049/26/12/3646 |
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