New terpyridine-containing macrocycle for the assembly of dimeric Zn(II) and Cu(II) complexes coupled by bridging hydroxide anions and π-stacking interactions

被引：34

作者：

Bazzicalupi, C ^{[1
]}

Bencini, A ^{[1
]}

Berni, E ^{[1
]}

Bianchi, A ^{[1
]}

Danesi, A ^{[1
]}

Giorgi, C ^{[1
]}

Valtancoli, B ^{[1
]}

Lodeiro, C ^{[1
]}

Lima, JC ^{[1
]}

Pina, F ^{[1
]}

Bernardo, MA ^{[1
]}

机构：

[1] Univ Florence, Dept Chem, Florence, Italy

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 16期

关键词：

D O I：

10.1021/ic049660l

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of the new terpyridine-containing macrocycle 2,5,8,11,14-pentaaza[15](6,6")cyclo(2,2':6',2")terpyridinophane (L) is reported. The ligand contains a pentaamine chain linking the 6,6" positions of a terpyridine unit. A potentiometric, H-1 NMR, UV-vis spectrophotometric and fluorescence emission study on the acid-base properties of L in aqueous solutions shows that the first four protonation steps occur on the polyamine chain, whereas the terpyridine nitrogens are involved in proton binding only at strongly acidic pH values. L can form both mono- and dinuclear Cu(II), Zn(II), Cd(II), and Pb(II) complexes in aqueous solution. The crystal structures of the Zn(II) and Cd(II) complexes {[ZnLH](2)(mu-OH)}(ClO4)(5) (6) and {[CdLH](2)(mu-Br)}(ClO4)(5).4H(2)O (7) show that two mononuclear [MLH](3+) units are coupled by a bridging anion (OH- in 6 and Br- in 7) and g-stacking interactions between the terpyridine moieties. A potentiometric and spectrophotometric study shows that in the case of Cu(II) and Zn(II) the dimeric assemblies are also formed in aqueous solution containing the ligand and the metals in a 1:1 molar ratio. Protonation of the complexes or the addition of a second metal ion leads to the disruption of the dimers due to the increased electrostatic repulsions between the two monomeric units.

引用

页码：5134 / 5146

页数：13

共 113 条

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