Synthesis, structural diversity and properties of metal(Mn, Ni, Zn) coordination polymers with 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene

• Main Authors: Wei-zeng Lin, 林威仁
• Other Authors: 王志傑
• Format: Others
• Language: zh-TW
• Published: 2008
• Online Access: http://ndltd.ncl.edu.tw/handle/wtvdtm

碩士 === 東吳大學 === 化學系 === 96 === Abstract We used 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (4-bpd) and KSCN to synthesis six crystals with three kinds of Mixed-Ligands Metal Coordination Polymers. (A) [Mn(4-bpd)(NCS)2(H2O)2]×2.5(4-bpd)��2(H2O)��(C2H5OH) (B) [Zn(4-bpd)(NCS)2]×(C2H5OH) (C1) [Ni(4-bpd)2(NCS)2]��3(C2H5OH)��(H2O) (C2) [Ni(4-bpd)2(NCS)2]��2(C2H5OH)��2(H2O) (C3) [Ni(4-bpd)2(NCS)2]��2(CH3CN)��(H2O) (C4) [Ni(4-bpd)2(NCS)2]��2((CH3)3COH)��3(H2O) The assembly reaction of M+2 ( Mn+2、Zn+2 ) with the Schiff base ligand, 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (4-bpd) and KNCS gave two crystals (A) and (B). The reaction of the 4-bpd ligand with Zinc(II) and Manganese(II) in C2H5OH/H2O generated 3-D structure of [Mn(4-bpd)(NCS)2(H2O)2]×2.5(4-bpd)��2(H2O)��(C2H5OH) (A) and [Zn(4-bpd)(SCN)2]×(C2H5OH) (B) respectively. The two 3D structures result from the weak hydrogen-bonding between 1-D chains. For Nickel(II), there are four types of crystal structure different from (A) and (B). Interesting to these four crystals, their coordinate environment around the Nickel(II) are similar. While they have the same formula of [Ni(4-bpd)2(NCS)2]�V. C1 and C2 , C3 and C4 were produced in the C2H5OH/H2O , CH3CN/H2O and ((CH3)3COH)/H2O, respectively. The solvent C2H5OH/H2O generated two different crystal in one-pot [Ni(4-bpd)2(NCS)2]��3(C2H5OH)��(H2O) (C3), which adopts a 2D 44 square-grid MOF and [Ni(4-bpd)2(NCS)2]��2(C2H5OH)��2(H2O) (C4), which adopts a 3D 658 CdSO4 MOF. We also formed [Ni(4-bpd)2(NCS)2]��2(CH3CN)��(H2O) (C5) with the solvent CH3CN/H2O, It adopts a 2D 44square-grid MOF the same as (C3). And the solvent ((CH3)3COH)/H2O generated the crystal [Ni(4-bpd)2(NCS)2]�� 2((CH3)3COH)��3(H2O) (C6) which adopts a 2D 44 square-grid MOF. For (C3) (C4) (C5) (C6) with the same chemical formula, the solvent system affect the final topology.