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Rajendiran Thekkel M. Kannappan Ramu Mahalakshmy Rajaram Rajeswari Janarthanam Venkatesan Rangarajan Rao Pillutla 《Transition Metal Chemistry》2003,28(4):447-454
A series of binuclear CuII complexes [Cu2XL]
n+ having two copper(II) ions bridged by different motifs (X = OH–, MeCO2
–, or Cl–) have been prepared using the ligands: H2L1 = 4-methyl-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H2L2 = 4-nitro-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H2L3 = 4-methyl-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol and H2L4 = 4-nitro-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol. The complexes have been characterized by spectroscopic, analytical, magnetic and electrochemical measurements. Cryomagnetic investigations (80–300 K) revealed anti-ferromagnetic exchange between the CuII ions (–2J in the range –50 to –182 cm–1). The strength of anti-ferromagnetic coupling lies in the order: OAc > OH > Cl. Cyclic voltammetry revealed the presence of two redox couples, assigned to CuII/CuII/CuII/CuI/CuI/CuI. The first reduction potential is sensitive to electronic effects from the aromatic ring substituents and steric effect on the donor nitrogens (side arm) of the ligand systems. 相似文献
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Rajendiran Thekkel M. Mahalakshmy Rajaram Kannappan Ramu Rajeswari Janarthanam Venkatesan Rangarajan Rao Pillutla 《Transition Metal Chemistry》2003,28(3):280-287
Binuclear CuII complexes having new flexible heptadentate ligands 2,6-bis{[bis(3,3-N,N-dimethylaminopropyl)amino]methyl}-4-bromophenol [HL1], 2,6-bis(3,3-N,N-dimethylaminopropyl)amino]methyl}-4-methylphenol [HL2], and 2,6-bis{[bis(3,3-N,N-dimethylaminopropyl)amino]methyl}-4-methoxyphenol [HL3], capable of assembling two copper ions in close proximity have been synthesized. Comparisons of the charge-transfer (CT) features, observed in electronic spectra of these complexes, are correlated with the electronic effect on the aromatic ring of the ligand systems. Cyclic voltammetry has revealed the existence of two reduction couples,
The first is sensitive to the electronic effects of aromatic ring substituents of the ligand system, shifting to more positive potentials when more electrophilic groups replace the existing substituents. The conproportionation constants (k
con) for the mixed valent CuICuII complexes have been determined electrochemically. The magnetic susceptibilities of the complexes have been measured over the 70–300 K range and the exchange coupling parameter (–2J) determined by a least squares fit of the data which indicates an antiferromagnetic spin exchange (–2J = 94–172 cm–1) between the CuII ions with bridging units in the order: N3 NO2 > OAc > OH. 相似文献
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