A series of ferrocenylimine [(£b5-C5H5)Fe(£b5-C5H4-C(Me)=N-R)]¡AR= nhexyl(1a)¡Acyclohexyl(1b)¡Aphenyl(1c)¡AN,N-dimethylethylamino(1d) ¡A4-methoxyphenyl(1e)¡A4-nitrophenyl(1f)¡Aand 2-methoxyethyl(1g)¡Ahave been synthesized by reaction of acetylferrocene and the corresponding amines through condensation reaction. Also 1,1¡¦-ferrocenyldiimines [Fe{(£b5-C5H4)-C(Me)=N-R}2]¡AR= nhexyl(2a)¡Acyclohexyl(2b)¡Aphenyl(2c)¡AN,N-dimethylethylamino(2d)¡A4-methoxyphenyl(2e)¡A4-nitrophenyl(2f)¡A3-nitrophenyl(2g)¡A2-methoxyethyl(2h) have been synthesized by reaction of 1,1¡¦-diacetylferoocene and the corresponding amines through condensation reaction. Solid state crystal X-ray structural analysis revealed the geometry of the ferrocene derivatives are various with the different substituents . In addition, these ferrocene derivatives might coordinate with CuBr to form a series of iminoferrcenyl copper(¢¹) complexes. Solid state crystal X-ray structural analysis revealed the iminoferrcenyl copper(¢¹) complexes 3a~3d showed monomeric or dimeric geometry and diiminoferrcenyl copper(¢¹) complexes 4a~4d exhibited polymeric or dimeric geometry.
All synthesized ferrocenylimine and1,1¡¦-ferrocenyldiimines derivatives exhibited a reversible one ¡Velectron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, £mp was quite well, with a correlation
coefficient of 0.96 in CH2Cl2 and CH3CN. According to the cyclic voltammograms, iminoferrocenyl copper complexes showed that the substituents on the imino parts strongly affect the redox potentials of the iron centers in the ferrocenyl segments as well as the copper metal center. The Cu+/Cu2+ couple redox potentials are in the range of 0.269V and 0.719V dependent on solvent effect.
The iminoferrocenyl copper complexes¡¦s UV-vis absorption seems to be red shift comparing with iminoferrocene. In the CH2Cl2, compound 3a¡B3b¡B4d shows emission at £fmax ~ 408 nm . In the CH3CN, compound 3a¡B3b¡B3c¡B3d¡B4a¡B4b and 4c show the blue shift emission band comparing with iminoferrocenyl copper complexes in CH2Cl2.
In addition, complex 4d in CH2Cl2 and complex complex 3d in CH3CN showed higher quantum yield value.
Moreover, compound 1a and 2a combined with CuBr exhibit good catalytic activity and controlling ability in the MMA ATRP process.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0721109-021359 |
| Date | 21 July 2009 |
| Creators | Tsai, Ming-chen |
| Contributors | Ting-Yu Lee, Teng-Yuan Dong, Lan-Chang Liang |
| Publisher | NSYSU |
| Source Sets | NSYSU Electronic Thesis and Dissertation Archive |
| Language | Cholon |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0721109-021359 |
| Rights | withheld, Copyright information available at source archive |
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