Studies On Multinuclear Manganese Complexes Modified By Ferrocenyl Group

The chemistry of manganese has been especially well developed in recent years because manganese is catalytically active in a variety of metalloenzymes. Poly (manganese carboxylate) complexes have become an important research field for the simulation of relevant manganese enzymes and the exploration of magnetism. Ferrocenecarboxylato is a good ligand with redox-active group that may influence the magnetic interaction between metal center of the complexes. What had been studied previously were reviewed in detail in this paper. Using ferrocenecarboxylato and other neutral ligand, we synthesized five manganese complexes. The complexes have been characterized by IR spectral elemental analysis and crystal X-ray diffraction. The magnetic properties of some complexes have been studied. Main work is listed as follows.1.A dinuclear manganese complex with 1,10-phen and ferrocenecarboxylato as ligands has been synthesized. The complex has been characterized by IR spectral and elemental analysis. The single crystal X-ray diffraction shows that the complex crystallized in the triclinic space group P3(2) with a=11.4332(5)?, b=11.433 ?, c = 37.5044(15)?,γ=120°,V=4245.7(3) ?3 , Z=3. Two manganese ions were bridged together by three ferrocenecarboxylatoes. The variable temperature solid magnetic susceptibility indicates the existences of a weak antiferromagnetic coupling of Mn(Ⅱ) pairs at low temperature. 2.A trineclear manganese complex with 2,2′-bpy and ferrocenecarboxylato as ligands has been synthesized. The structure has been characterized by IR spectra, elemental analysis. Single crystal X-ray diffraction shows that the complex crystallized in the triclinic space group Pī with a=11.4559(6)?, b=13.0128(7)?, c=14.8930(8)?, α=109.4000(10)o, β=111.7660(10)o,γ=97.4070(10)o, V=1862.53(17)?3 , Z=2. There are two types of bridging ferrocenecarboxylato ligands in the molecule. The three manganese ions arrange in is a line. The variable temperature solid magnetic susceptibility of the complex shows the existences of intramolecular weak antiferromagnetic interaction at low temperature.3. A tetranuclear manganese complex with 2,2′-bpy and ferrocenecarboxylato as ligands has been prepared by controlling the ratio of the reagents. The structure has been characterized by IR spectra and single crystal X-ray diffraction. The result shows that the complex crystallized in the monoclinic space group I2/a with a=33.908(3)?, b=22.0836(10)?, c= 34.991(3)?,β=112.371(9)o, V=24229(3)?3 , Z=8. There is a butterfly [Mn4O2]8+ structural cluster core in the molecule. The valence of each manganese ion is +3. The coordination mode of all the ferrocenecarboxylatoes is μ2-O2CFc.4. A one-dimensional structure coordination polymer of manganese with ferrocenecarboxylato as ligand has been synthesized. The structure has been characterized by IR spectral, elemental analysis and single crystal X-ray diffraction. The result shows that the complex crystallized in the triclinic space group Pī with a= 11.9256(7)?, b=12.0542(7)?, c=13.0976(8)?, α=88.4100(10)o, β=78.9410(10)o, γ=63.5120(10)o, V=1650.30(17)?3 , Z=1. There is a [Mn2(O2CFc)4] subunit in the chain that two manganese ions were bridged by four ferrocenecarboxylatoes. The variable temperature solid magnetic susceptibility shows the existences of intramolecular weak antiferromagnetic interaction.5. A two-dimensional structure coordination polymer of manganese with ferrocenecarboxylato and 4,4′-bpy as bridging ligands has been synthesized. The complex has been characterized by IR spectra, elemental analysis and single crystal X-ray diffraction. The result shows that the complex crystallized in the triclinic space group Pī with a=10.9802(7)?, b=11.4929(7)?, c=14.8800(9)?,α=82.3570(10)o, β=83.4290(10)o, γ=65.9560(10)o, V=1695.84(18)?3 , Z=2. There are two types of ferrocenecarboxylato displaying different coordination modes in the molecule. The one-dimensional chain that bridged by ferrocenecarboxylatoes were linked by 4,4′-bpy to form the two dimensional structure. The result o...