Charge separation in metallomacrocycle complexes linked with electron acceptors by axial coordination
Charge separation in metallomacrocycle complexes linked with electron acceptors by axial coordination
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DOI：
10.1039/b901191a
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发表时间：
2009-01-01
影响因子：
4
通讯作者：
Kojima, Takahiko
中科院分区：
文献类型：
--
作者：
Fukuzumi, Shunichi;Honda, Tatsuhiko;Kojima, Takahiko
一种简单而优雅的方法来获得连接的给体-受体实体，其中包括具有固定距离和取向的金属大环配合物，即利用轴向配体与金属大环配合物配位。利用中心硅原子的六配位性质，通过连接两个电子受体单元，富勒烯SIPC-(C-60)(2)，三硝基荧光酮SIPC-(肿瘤坏死因子)(2)和三硝基二氰亚甲基荧烯SIPC-(TNDCF)(2)，容易地合成了一系列含电子受体的三元硅酞菁(SIPC)。吡啶基萘二亚胺(PyNIm)的氮能与锌的金属中心配位，形成一种给体-受体络合物：ZnTPP-PyNIm。卟啉环的扭曲大大增强了吡啶基团与锌卟啉络合物的结合。利用八苯基酞菁锌(ZnOPPc)和二质子化十二苯基卟啉(H4DPP2+)的鞍形变形，利用4-吡啶甲酸酯(4-PyCOO-)的轴向配位键和氢键，得到了由锌(OPPc)和H4DPP2+组成的离散超分子组装。描述了这些金属大环中的电荷分离，以及在发展超分子太阳能电池方面的应用。
A simple but elegant way to obtain linked donor-acceptor entities involving metallomacrocycle complexes with fixed distance and orientation is the use of coordination of axial ligands to metallomacrocycle complexes. A series of electron acceptor-bearing silicon phthalocyanine (SiPc) triads have been readily synthesized, using the six-coordinated nature of the central silicon atom, by attachment of two electron-acceptor units, fullerene SiPc-(C-60)(2), trinitrofluorenone SiPc-(TNF)(2) and trinitrodicyanomethylenefluorene SiPc-(TNDCF)(2). The nitrogen of pyridylnaphthalenediimide (PyNIm) can coordinate to the metal center of zinc porphyrin to form a donor-acceptor complexes: ZnTPP-PyNIm. The binding of pyridine moieties to Zn-porphyrin complexes is much enhanced by the distortion of porphyrin ring. By taking advantage of saddle distortion of zinc octaphenylphthalocyanine (ZnOPPc) and diprotonated dodecaphenylporphyrin (H4DPP2+), a discrete supramolecular assembly composed of Zn(OPPc) and H4DPP2+ and is obtained by using 4-pyridinecarboxylate (4-PyCOO-) with the axial coordination bond and hydrogen bonding. The charge separation in these metal macrocycles linked with electron acceptors with axial coordination bonds is described together with the application to develop supramolecular solar cells.