Yoshimoto Soichiro, Suto Koji, Tada Akinori, Kobayashi Nagao, Itaya Kingo
Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aoba-yama 04, Sendai 980-8579, Japan.
J Am Chem Soc. 2004 Jun 30;126(25):8020-7. doi: 10.1021/ja048760n.
Adlayers of 15-crown-5-ether-substituted cobalt(II) phthalocyanine (CoCRPc) were prepared by immersion of either Au(111) or Au(100) substrate into benzene-ethanol (9:1 v/v) mixed solutions containing CoCRPc. In situ STM imaging was carried out after transferring the CoCRPc-modified Au crystals into aqueous HClO(4) solution. The packing arrangement of the CoCRPc array on Au(111) was determined to be p(8 x 4 radical 3R - 30 degrees ), and the internal structure was clearly observed by high-resolution STM. Two adlayer structures of CoCRPc, (8 x 9) and (4 radical 5 x 4 radical 5)R26.7 degrees, were found on the Au(100)-(1 x 1) terrace. In the presence of 1 mM Ca(2+), two Ca(2+) ions were trapped in two diagonally located 15-crown-5-ether moieties of each CoCRPc molecule on Au(111), whereas encapsulation of Ca(2+) ions was not seen in the CoCRPc arrays on the Au(100)-(1 x 1) surface. The present study demonstrates that the relationship between crown moieties of CRPc and the underlying Au lattice is important in the trapping of Ca(2+) ions in crown rings.
通过将Au(111)或Au(100)基底浸入含有15 - 冠 - 5 - 醚取代钴(II)酞菁(CoCRPc)的苯 - 乙醇(9:1 v/v)混合溶液中来制备CoCRPc的吸附层。将CoCRPc修饰的金晶体转移到HClO(4)水溶液中后进行原位STM成像。确定CoCRPc阵列在Au(111)上的堆积排列为p(8×4√3R - 30°)，并且通过高分辨率STM清晰地观察到了内部结构。在Au(100)-(1×1)台面上发现了CoCRPc的两种吸附层结构，即(8×9)和(4√5×4√5)R26.7°。在存在1 mM Ca(2+)的情况下，两个Ca(2+)离子被困在Au(111)上每个CoCRPc分子的两个对角位置的15 - 冠 - 5 - 醚部分中，而在Au(10)- (1×1)表面的CoCRPc阵列中未观察到Ca(2+)离子的包封。本研究表明，CRPc的冠醚部分与下层金晶格之间的关系对于Ca(2+)离子在冠醚环中的捕获很重要。
