Crystal Retro-Engineering: Structural Impact on Silver(I) Complexes with Changing Complexity of Tris(pyrazolyl)methane Ligands
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- 作者：Daniel L. Reger ; Radu F. Semeniuc ; Christine A. Little ; Mark D. Smith
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：September 18, 2006
- 年：2006
- 卷：45
- 期：19
- 页码：7758 - 7769
- 全文大小：610K
- 年卷期：v.45,no.19(September 18, 2006)
- ISSN：1520-510X
文摘
The preparation and structures of seven new silver(I) complexes involving the parent tris(pyrazolyl)methane unit,[C(pz)3], as the donor set, {[C6H5CH2OCH2C(pz)3]Ag}(BF4), {[C6H5CH2OCH2C(pz)3]2Ag3}(CF3SO3)3, {[HOCH2C(pz)3]Ag}(BF4), {[HOCH2C(pz)3]Ag}(CF3SO3), {[HC(pz)3]2Ag2(CH3CN)}(BF4)2, {[HC(pz)3]Ag}(PF6), and{[HC(pz)3]Ag}(CF3SO3), are reported. This project is based on a retro-design of our multitopic C6H6-n[CH2OCH2C(pz)3]n(pz = pyrazolyl ring, n = 2, 3, 4, and 6) family of ligands in such a way that each new ligand has one fewerorganizational feature. The 
2-1 bonding mode of the [C(pz)3] units to two silvers, also observed with the multitopicligands, is the dominant structural feature in all cases. Changing the counterion has important effects on the localstructures and on crystal packing. When these structures are compared to similar ones based on the multitopicC6H6-n[CH2OCH2C(pz)3]n ligands, it has been shown that the presence of the rigid parts (central arene core andthe [C(pz)3] units) are important in order to observe highly organized supramolecular structures. The presence ofthe flexible ether linkage is also crucial, allowing all noncovalent forces to manifest themselves in a cumulative andcomplementary manner.
2-1 bonding mode of the [C(pz)3] units to two silvers, also observed with the multitopicligands, is the dominant structural feature in all cases. Changing the counterion has important effects on the localstructures and on crystal packing. When these structures are compared to similar ones based on the multitopicC6H6-n[CH2OCH2C(pz)3]n ligands, it has been shown that the presence of the rigid parts (central arene core andthe [C(pz)3] units) are important in order to observe highly organized supramolecular structures. The presence ofthe flexible ether linkage is also crucial, allowing all noncovalent forces to manifest themselves in a cumulative andcomplementary manner.