Dissertation
Dissertation > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )

Syntheses, Structures and Characterizations of Polynuclear Copper(II) Complexes

Author ChengDeYi
Tutor ZhengYueQing
School Ningbo University
Course Inorganic Chemistry
Keywords Multi - core copper cluster Hydroxy bridged Dicarboxylic acid Phosphate Crystal structure
CLC O641.4
Type Master's thesis
Year 2008
Downloads 151
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The multi-core copper complexes has important theoretical and potential applications in the design and research of the exploration of molecular-based magnetic materials, the development of new catalysts and multicore copper metal enzyme mimics, has been a hot research topic, one of the people. The papers in the literature review section of recent years, published more than 170 articles on copper (II) complexes of literature reviewed the classification of multi-core copper skeleton, summed up the corresponding Hamiltonian operator and the van Vleck Magnetic chemical equation, and provides an overview of the latest research of electrochemical, catalytic, and biological activity of the copper (II) complexes as well as the main strategy of the synthesis of multi-core copper complexes. The subsequent part of the paper reported that the laboratory application of spontaneous self-assembly synthesized with different multicore copper skeleton thirteen kinds of new copper (II) complex: {[Cu 4 (bpy) 4 (OH) 4 (H 2 O) 2 ]} (NO 3 ) < sub> 2 (C 5 H 6 O 4 ) · 8H 2 O (1) , {[Cu 4 (bpy) 4 (OH) 4 (H 2 O) 2 ]} (C 5 H 6 O 4 ) 2 · 16H 2 < / sub> O (2), {[Cu 4 (bpy) 4 (OH) 4 (H 2 O) 2 ]} (C 8 H 4 O 4 ) 2 · 6H 2 O (3), {[Cu 4 (bpy) 4 (OH) 4 (H 2 O) 2 ]} (NO 3 ) 2 (C 7 H 5 O 2 ) 2 · 6H 2 O (4), {[Cu 6 (bpy) 6 (OH) 6 - (H 2 O) 2 ]} (C 6 H 8 O 4 ) 3.23 H 2 O (5), {[Cu 6 (bpy) < sub> 6 (OH) 4 (NO 3 ) 2 ]} (NO 3 ) 4 · 5H 2 O (6), {[Cu (phen) 2 ] 2 (C 6 H 8 O 4 )} (ClO 4 ) 2 (7), { [Cu (phen) 2 ] 2 (C 6 H 8 O 4 )} (ClO 4 ) 2 · 1.33H 2 O (8), {[Cu 2 (phen ) 2 (H 2 O)] 2 (C 6 H 8 O 4 ) 2 } (ClO 4 ) 4 (9), {[Cu 2 (bpy) 2 (H 2 O)] 2 (C 6 H 8 < / sub> O 4 ) 2 } (ClO 4 ) 4 · 2H 2 O (10), [Cu 4 (H 2 O) 2 (phen) 4 (μ4- PO 4 ) 2 (μ2-O)] · 11H 2 O (11), [Cu 4 ( bpy) 4 (μ4-PO 4 ) 2 (μ2-Cl) 2 ] · 10H 2 O (12), [Cu 2 (bpp) 4 (H 2 PO 4 ) 2 ] (HPO 4 ) · H 2 O (13) (bpy = 2,2 - bipyridine, phen = 1,10 - phenanthroline, bpp = 1,3 - two (4 - pyridyl) propane (C 5 H 6 O 4 ) the 2 - = glutaric ion (C 6 H 8 O 4 ) 2 - = adipic acid ions, (C 7 H 5 O 2 ) 2 - = benzoate ions (C 8 H 4 O 4 ) 2 - = terephthalic acid ion), and the single crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, differential thermal gravimetric analysis, reported the characterization results of the magnetic chemical and electrochemical methods. Stepped skeleton hydroxy bridged tetranuclear copper with six nuclear copper complexes 1-6 from alkaline conditions the of Cu 2 , 2,2 '- bipyridine carboxylic acid or dicarboxylic acid spontaneous self-assembly. Complexes 1-4 and complex characteristics of the structural units were stepped quad-core copper [Cu 4 (bpy) of 4 (μ2-OH) 2 (μ3-OH) 2 (H 2 O) 2 ] 4 with cationic and ladder six-core copper [Cu 6 (bpy) 6 (μ2-OH) 2 (μ3-OH) 4 (H 2 O) 2 ] 6 complex cations, each Cu atom is located in the five-coordinate square-pyramidal geometry, outermost Cu atoms in the axial sites occupied by the water molecules of the ligand, while the characteristic structure of the complex 6 unit is a tetravalent six-core copper ladder of [Cu 6 (bpy) 32 6 (μ2-OH) 2 (μ3-OH) 4 (NO 3 ) 2 ] 4 with cation. Unlike complexes 5 and 6 with cations bidentate bridging NO 3 - ions with the most outer side of the two Cu atom ligand, complexes, making Cu atoms in the five-coordinate Quartet The cone and hexacoordinated elongated octahedral geometry environment. Studies have shown that + π??? The π role to play an important role in the stability of the ladder multicore copper skeleton. Between the complex cations π??? Π role with the matter 1-6 with cationic assembled to form a two-dimensional supramolecular layer has a porous structure and crystallization water molecules and counter anions through extensive hydrogen bonds to form a three-dimensional hydrogen bond The network structure, and complex cations supramolecular layers interspersed with each other. Magnetic analysis showed that the ferromagnetic coupling between the quad-core copper skeleton copper ion, while the six-core copper skeleton overall performance antiferromagnetic coupling. To Cu (ClO in 4 ) 2 · 6H 2 O, adipic acid and 1,10 - o-phenanthroline morpholine or 2,2 - bipyridine as raw material was obtained by adjusting the pH of the solution or the substance molar ratio synthesis complexes 7-10. Dumbbell-shaped complexes 7 and 8 contain adipic acid bridged binuclear copper {[Cu (phen) 2 ] 2 (C 6 H 8 O 4 )} 2 complex cations, they are due to the formation of the the double interpenetrating (4,4) grid type Aromatic Ring Stacking supramolecular structure, the counterion of the perchlorate ion and the presence of crystallization water molecules are filled in the cavities. Complex 9 tetranuclear copper cluster primitive type with double-10 semi-paddle-the wheel (DSPW) can be regarded as a dimer of two semi-paddle-wheel (SPW) type binuclear copper unit. Quad-core copper clusters as connected to the structure of four sub-element by adipate bridged form a pore structure (4,4) grid-type two-dimensional coordination polymer, perchlorate ions and water molecules fill the pore of . Magnetic measurements show that the build binuclear copper unit SPW tetranuclear copper clusters with antiferromagnetic coupling between the copper ions, and is located in the middle of the quad-core copper cluster Cu 2 O 2 < / sub> two μ2-O atoms in the four-membered ring on the bridging between the copper ions showed a weak ferromagnetic coupling effect. Complexes 9 and 10 are in the range of -1.2-0.8 V with two quasi-reversible redox pairs, the redox processes show that its structure is different coordination environments of copper ions is likely to CuIICuII? CuIICuI? CuICuI the form of step-by-step carried out. The formation of complexes in methanol / water mixed solvent of CuCl 2 · 2H 2 O, phosphate and 1,10 - phenanthroline or 2,2 - bipyridine reaction 11 and 12. Both contain phosphate bridge linking the quad-core copper complex molecules the of Cu 4 (H 2 O) 2 (phen) 4 (μ4-PO 4 ) 2 (μ2-O)] and [Cu 4 (bpy) 4 (μ4-PO 4 ) 2 (μ2-Cl) 2 ]. Molecular network supramolecular layer, and crystallization water molecules located between supramolecular layer formed through aromatic ring stacking interactions. Further, in a methanol / water mixed solvent, the Cu (OH) 2 , 1,3 - two (4 - pyridyl) propane reacted with phosphoric acid to form complexes 13, Cu (II) ion through the pyridine propane ligand bridged to a two-dimensional layer structure is formed, which are parallel to the (011) and (101) plane and having a pore structure is formed double interspersed network, hydrogen phosphate ions with water molecules and filled in the pores by hydrogenolysis key role interconnected.

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