自組裝合成竹型膠囊狀錸金屬超分子與含triazole 配位聚合物之研究

Synthesis of Rhenium-Based Bamboo-Type Capsule and Triazole-Containing Inorganic-Organic Hybrid Materials

廖士豪(Shih-Hao Liao)

指導教授 ： 曾添文

國立臺北科技大學/工程學院/化學工程研究所/碩士(2009年)

https://doi.org/10.6841/NTUT.2009.00095

摘要

本論文分成兩大部分加以敘述 (一)錸金屬膠囊狀化合物之超分子 本研究以自組裝法製備竹型膠囊狀超分子。設計提供三個電子配基以螯合方式配位於fac-(CO)3Re 之形成竹節，並與能提供兩個電子之架橋配基結合形成竹壁，滿足錸金屬十八個電子的穩定組態，構築具有竹型膠囊狀之新型電中性錸金屬超分子。Re2(CO)10 與配基2,3-di(4-pyridyl)-2,3-butanediol(dpbd)、tetrahydroxy-p-benzoquinone dihydrate (thbq) 於對二甲苯溶液中，以水熱法反應得到化合物[{Re(CO)3}6(bho)(acpy)6]·C8H10 (1)。在反應過程中dpbd 氧化並從中斷裂成兩個4-acetylpyridine (acpy, C7H7NO)，而 thbq 配子還原成benzene-1,2,3,4,5,6-hexaolate (C6O66-, bho)，且以 bho 螯合六個錸金屬形成獨特的竹型膠囊狀超分子化合物，具有六芒星結構，化合物1 在膠囊內嵌入對二甲苯。若以鄰二甲苯或間二甲苯為溶劑，在相似反應條件下，得化合物{Re(CO)3}6(bho)(acpy)6 (2)，該化合物無任何客分子，竹型膠囊呈閉環狀。且化合物2 不能因加入對二甲苯而轉換成化合物1。這顯示化合物1 在形成過程中，同時將對二甲苯容納於膠囊結構中，且化合物1 對於客分子p-xylene 具有專一性。化合物1 與2 均以IR、EA、NMR、UV 和單晶X 光繞射鑑定結構。 (二)含triazole 配子自組裝合成配位聚合物 探討以2-amino-5-carboxylic acid-1,3,4-triazole (AmTAZAc, C3H2N4O2)與鎘離子，於不同pH 值下作自組裝反應，合成配位聚合物[Cd(AmTAZAc)H2O]n (3)，[Cd(AmTAZAc)4(H2O)5]n (4) ，以單晶X-ray 繞射解析結構並探討其性質。

關鍵字

自組裝 ； 超分子 ； 錸金屬 ； 膠囊狀化合物 ； 配位化合物

並列摘要

Rhenium-based bamboo-type capsule and coordination polymers were synthesized using a self-assembly strategy with complete structural were characterization. The content of this thesis can be summarized as follows:
(1) Self-assembly of the rhenium-based bamboo-type capsules,
[{Re(CO)3}6(bho)(acpy)6]·C8H10 (1) and {Re(CO)3}6(bho)(acpy)6 (2) from Re2(CO)10 and tetrahydroxy-p-benzoquinone dihydrate (thbq) in the presence of 2,3-di(4-pyridyl)-2,3-butanediol (dpbd) under solvothermal conditions is described. under the reaction conditions, the dpbd ligand was first oxidized to 4-acetylpyridine (acpy, C7H7NO) ligand. Each thbq ligand was coordinated to six {Re(CO)3}6(C7H7NO)6 moieties, which acted as edges, thereby forming hexarhenium(I) complexes 1, 2 as bamboo-type capsules. This synthetic approach allows the preparation of highly
symmetrical nanostructures. These compounds were analyzed by IR, EA, TGA, NMR, UV, and PL.
(2) Synthesis of coordination polymers based nanometer-sized inorganic-organic hybrid materials [Cd(C3H2N4O2)H2O]n (3) and [Cd(C3H2N4O2)4(H2O)5]n (4) carried out by self-assembly of 2-amino-5-carboxylic acid-1,3,4-triazole (C3H2N4O2, AmTAZAc) and cadmium ion. The structures of compound 3, 4 were characterized by single-crystal X-ray diffraction analysis. Under high pH (12.40) 2D structure of 3 was obtained, while at a lower pH of less than 10.47, a 3D structure of compound 4 was achieved. The thermal stabilities and photophysical properties had also been studied.

並列關鍵字

Self-assembly ； supramolecule ； coordination polymers ； rhenium ； capsule

參考文獻

1. Millward, A. R.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 17998.

2. Prakash, M. J.; Radhakrishnan, T. P. Chem. Mater. 2006, 18, 2943.

4. (a) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O'Keeffe, M.; Yaghi, O. M.; Science 2003, 300, 1127. (b) Tang, E.; Dai, Y.-M.; Zhang, J.; Li, Z.-J.; Yao, Y.-G.; Zhang, J.; Huang, X.-D. Inorg. Chem. 2006, 45, 6276.

7. Rajendran, T.; Manimaran, B.; Lee, F. Y.; Lee, G. H.; Peng, S. M.; Wang, C. M.; Lu, K. L. Inorg. Chem. 2000, 39, 2016.

9. (a) Dinca, M.; Long, J. R. Angew. Chem. Int. Ed. 2008, 47, 6766. (b) Furukawa,