Assembly of Hybrid Inorganic-Organic Materials from Octahedral Nb6 Clusters and Metal Complexes
详细信息 查看全文
- 作者：Huajun Zhou ; Cynthia S. Day ; and Abdessadek Lachgar
- 刊名：Chemistry of Materials
- 出版年：2004
- 出版时间：November 30, 2004
- 年：2004
- 卷：16
- 期：24
- 页码：4870 - 4877
- 全文大小：371K
- 年卷期：v.16,no.24(November 30, 2004)
- ISSN：1520-5002
文摘
The octahedral edge-bridged niobium cyano-chloride cluster [Nb6Cl12(CN)6]4- and the [Mn(salen)]+ metal complex have been used as building units to prepare solid-state materialswith extended frameworks at room temperature through self-assembly processes. Threematerials with different dimensionalities were prepared and characterized: (Me4N)4[Nb6Cl12(CN)6]·2MeOH (1) (0D), (Me4N)2[Mn(salen)]2[Nb6Cl12(CN)6] (2) (2D), and (Et4N)2[Mn(salen)(MeOH)]2[Nb6Cl12(CN)6]·2MeOH (3) (1D). 1 was used as cluster precursor for thepreparation of 2 and 3. The framework dimensionality seems to be affected by the size ofthe template-counterion used. Single-crystal X-ray analysis revealed that 1 is based ondiscrete [Nb6Cl12(CN)6]4- separated by (Me4N)+ and MeOH molecules. 2 has a two-dimensional framework, in which each layer is formed by [Nb6Cl12(CN)6]4- clusters connectedthrough four cyanide ligands to four different [Mn(salen)]+. Each manganese complexconnects two clusters through Nb-CN-Mn-NC-Nb bridges, leading to the formation ofanionic layers interleaved by (Me4N)+. In 3, every cluster unit [Nb6Cl12(CN)6]4- is linked totwo [Mn(salen)(MeOH)]+ units through two apical trans cyanide ligands, leading to theformation of trimeric units {Mn-(NC)[Nb6Cl12(CN)4](CN)-Mn}. Every trimeric unit connectsto two neighboring units through hydrogen bonding between OMeOH from coordinatedmethanol ligand and NCN from two neighboring clusters, resulting in the formation of anionicchains along the crystallographic a axis {[Mn(salen)(MeOH)]2[(Nb6Cl12)(CN)6]}2-. The chainsare separated by (Et4N)+ and MeOH. Magnetic properties and thermal behavior of thesenew hybrid inorganic-organic compounds are presented.