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Structural Dependence of Aromatic Ring Stacking and Related Weak Interactions in Ternary Amino Acid-Copper(II) Complexes and Its Biological Implication
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Structures and stabilization due to stacking of ternarycopper(II) complexes containing an aromatic aminoacid(AA) and an aromatic diamine (DA), Cu(AA)(DA), have beeninvestigated by potentiometric, spectroscopic, andX-ray diffraction methods. For the systems with AA =para-X-substituted L-phenylalanine(L-XPhe; X = H,NO2, OH, NH2) and DA = 2,2'-bipyridine (bpy)or 1,10-phenanthroline (phen), the difference absorptionspectrain the region 320-400 nm exhibited a peak assignable to the chargetransfer interaction between the aromaticrings of DA and L-XPhe, the intensity being in the orderNH2 > OH > H NO2 with respect to X.The stabilityconstants of Cu(AA)(DA) determined for AA =DL-XPhe (X = F, Cl, Br) and L-XPhe (X =NH2, NO2, I) at 25C and I = 0.1 M (KNO3) indicated thatstabilization of Cu(L-XPhe)(DA) relative toCu(L-Ala)(en) (Ala = alanine;en = ethylenediamine) is in the order Br > OH > Cl NH2 > NO2 H F. The structures of[Cu(L-NH2Phe)(bpy)]NO3·H2O (1),[Cu(L-Tyr)(phen)]ClO4·2.5H2O(2),[Cu(L-Phe)(phen)]Cl·3H2O(3), and [Cu(L-Phe)(bpy)]ClO4·H2O (4), isolatedas crystals, were determined by the X-ray diffraction method:1, orthorhombic,P212121, a= 10.292(1) Å, b = 13.576(4) Å, c= 14.407(1) Å, V = 2012.9 Å3,Z = 4, R = 0.037, Rw= 0.038;2, orthorhombic,P212121, a= 18.20(2) Å, b = 32.63(1) Å, c= 8.14(1) Å, V = 4833 Å3,Z = 4, R = 0.111,Rw= 0.087; 3, monoclinic, P21,a = 11.738(2) Å, b = 16.301(1) Å,c = 11.795(1) Å, = 102.01(1),V = 2207.4Å3, Z = 2, R = 0.045,Rw = 0.035; 4, monoclinic,P21, a = 9.954(2) Å,b = 24.179(3) Å, c = 9.780(2) Å, =107.32(1), V = 2257.1 Å3,Z = 4, R = 0.065, Rw= 0.060. All of the complexes have a similardistortedsquare-pyramidal structure around the central Cu(II) ion.While 1 and 2 have a structure involvingaromatic ringstacking in the solid state, 4 has a structure without itand 3 has both types of structures in the unitcell.

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