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手性配位聚合物的构建由 V 型氧双苯甲酰基氨基酸衍生物:结构,磁性和光致发光性能。

Homochiral coordination polymers constructed from V-shaped oxybisbenzoyl-based amino acid derivatives: structures, magnetic and photoluminescence properties.

机构信息

School of Chemistry and Molecular Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, Shanghai 200241, P.R. China.

出版信息

Dalton Trans. 2018 Oct 9;47(39):13990-14000. doi: 10.1039/c8dt03093f.

Abstract

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.

摘要

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。

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