Two Porous Zinc Coordination Polymers with (10,3) Topological Features Based on a N-Centered Tripodal Ligand and the Conversion of a (10,3)-d Subnet to a (10,3)-a Subnet

Two porous (3,4)-connected zinc coordination polymers, {[Zn(TIPA)(mal)1/2](NO3)·3H2O}n (1) and {[Zn(TIPA)(glu)1/2](NO3)·H2O}n (2) (mal = malonic acid, glu = glutaric acid, TIPA = tris(4-(1H-imidazol-1-yl)phenyl)amine) have been hydrothermally synthesized and characterized. Complex 1 crystallizes in the orthorhombic space group Pnna (No. 52) containing an unusual 3D subnet with (10,3)-d topology and left- and right-handed helical channels. Complex 2 crystallizes in the orthorhombic chiral space group P2221 (No. 17) containing an unusual 3D chiral subnet with (10,3)-a topology and 4-fold right-handed helical channels. The conversion of achiral complex 1 with a (10,3)-d (utp) achiral subnet to chiral complex 2 with a (10,3)-a (srs) chiral subnet has been successfully induced by increasing the length of ditopic aliphatic dicarboxylic acid. Second harmonic generation (SHG) measurement was performed on complex 2 revealing that 2 has a strong SHG response, and the SHG efficiency is approximately 0.8 times that of urea (ca. 8 times that of KDP). In addition, photoluminescence and thermogravimetric analysis were also performed on 1 and 2.

两种多孔(3,4)-连接锌配位聚合物{[Zn(TIPA)(mal)₁/₂](NO₃)·3H₂O}ₙ(1)与{[Zn(TIPA)(glu)₁/₂](NO₃)·H₂O}ₙ(2)（其中mal为丙二酸(malonic acid)，glu为戊二酸(glutaric acid)，TIPA为三(4-(1H-咪唑-1-基)苯基)胺(tris(4-(1H-imidazol-1-yl)phenyl)amine)）经水热法合成并得到表征。配合物1结晶于正交晶系空间群Pnna（编号52），其结构包含具有(10,3)-d拓扑的非常规三维子网络，以及左手与右手螺旋通道。配合物2结晶于正交晶系手性空间群P222₁（编号17），其结构包含具有(10,3)-a拓扑的非常规三维手性子网络，以及四重右手螺旋通道。通过增加双齿脂肪族二羧酸的碳链长度，成功诱导实现了具有(10,3)-d（utp）非手性子网络的非手性配合物1向具有(10,3)-a（srs）手性子网络的手性配合物2的转化。对配合物2开展了二次谐波生成(Second harmonic generation, SHG)测试，结果显示其具有较强的二次谐波生成响应，该效率约为尿素的0.8倍（约为磷酸二氢钾(KDP)的8倍）。此外，还对配合物1与2分别进行了光致发光与热重分析。