School of Chemistry and Molecular Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, Shanghai 200241, P.R. China.
Dalton Trans. 2018 Oct 9;47(39):13990-14000. doi: 10.1039/c8dt03093f.
Five novel homochiral coordination polymers (HCPs) [Cu2(ODBALa)2(bpa)2H2O]·7H2O (1), [M(ODBALa)H2O]·H2O (M = Mn for 2; Co for 3), [Cu(ODBPRo)(bpe)]·7H2O (4) and [Cd2.5(ODBPRo)(HODBPRo)3(bpe)2.5]·13H2O (5) have been successfully synthesized by using designed chiral 4,4'-oxybisbenzoyl alanine/proline derivatives in the absence/presence of N-donor ancillary ligands, where H2ODBALa = 4,4'-oxybisbenzoyl-bis(l-alanine), H2ODBPRo = 4,4'-oxybisbenzoyl-bis(l-proline), bpa = 1,2-bis(4-pyridyl)ethane, and bpe = 1,2-bis(4-pyridyl)ethene. Interestingly, the combination of the chiral derivatives and metal ions gives various chiral metal-organic fragments, which are connected by N-donor ancillary ligands to construct the intriguing homochiral structures. In 1, 40-membered [Cu2(ODBALa)2] metallacycles as beads are strung by bpa ligands, yielding a one-dimension (1D) tortuous chain. Compounds 2 and 3 are isomorphous and possess a 3D metal-organic framework, embedding the unique (μ2-COO)(μ2-Ocarboxylate)(μ2-H2O) triple-bridges and twisted (-Mn4(ODBALa)4-)n left-handed helical chains. In 4, the [Cu(ODBPRo)]n left-handed helical chains are linked by bpe ligands to constitute a high undulated 2D layer. In 5, the crab-like [(Cd1)2(Cd2)(Cd3)2(HODBPRo)6(ODBPRo)2] fragments are joined together to form a 1D left-handed helical chain, which is further connected by bpe ligands to build a remarkable layered network. Magnetic susceptibility measurements of 2 and 3 indicate typical antiferromagnetic behaviour between the triple-bridging Mn(ii) ions in 2, whereas ferromagnetic coupling between the triple-bridging Co(ii) ions exists in 3. Moreover, the photoluminescent spectrum of 5 exhibits a strong solid-state emission at 414 nm.
五种新型的手性配位聚合物（HCPs）[Cu2（ODBALa）2（bpa）2H2O]·7H2O（1），[M（ODBALa）H2O]·H2O（M=Mn 为 2；Co 为 3），[Cu（ODBPRo）（bpe）]·7H2O（4）和[Cd2.5（ODBPRo）（HODBPRo）3（bpe）2.5]·13H2O（5）已通过使用设计的手性 4,4'-氧二苯甲酰丙氨酸/脯氨酸衍生物在不存在/存在 N-供体辅助配体的情况下成功合成，其中 H2ODBALa=4,4'-氧二苯甲酰基-双（l-丙氨酸），H2ODBPRo=4,4'-氧二苯甲酰基-双（l-脯氨酸），bpa=1,2-双（4-吡啶基）乙烷，和 bpe=1,2-双（4-吡啶基）乙。有趣的是，手性衍生物与金属离子的结合形成了各种手性金属有机片段，这些片段通过 N-供体辅助配体连接起来，构建了有趣的手性结构。在 1 中，40 元[Cu2（ODBALa）2]金属大环作为珠子被 bpa 配体串起来，形成一维（1D）扭曲链。化合物 2 和 3是同构的，具有三维金属有机骨架，嵌入独特的（μ2-COO）（μ2-O 羧酸酯）（μ2-H2O）三重桥和扭曲的（-Mn4（ODBALa）4-）n 左手螺旋链。在 4 中，[Cu（ODBPRo）]n 左手螺旋链通过 bpe 配体连接起来，构成了一个高起伏的 2D 层。在 5 中，蟹状[（Cd1）2（Cd2）（Cd3）2（HODBPRo）6（ODBPRo）2]片段连接在一起形成一维左手螺旋链，该链进一步通过 bpe 配体连接形成一个显著的层状网络。2 和 3 的磁化率测量表明，2 中三重桥接 Mn（ii）离子之间存在典型的反铁磁行为，而 3 中三重桥接 Co（ii）离子之间存在铁磁耦合。此外，5 的光致发光光谱在 414nm 处显示出强烈的固态发射。
