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R-Substituent-Induced Structural Diversity and Single-Crystal to Single-Crystal Transformation of Coordination Polymers: Synthesis, Luminescence, and Magnetic Behaviors
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2021-08-19 , DOI: 10.1021/acs.cgd.1c00491 Zhen Zhang 1 , Jie Zhou 1 , Han Xu Sun 1 , Mei He 1 , Wei Li 1 , Lin Du 1 , Mingjin Xie 1 , Qi-Hua Zhao 1
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2021-08-19 , DOI: 10.1021/acs.cgd.1c00491 Zhen Zhang 1 , Jie Zhou 1 , Han Xu Sun 1 , Mei He 1 , Wei Li 1 , Lin Du 1 , Mingjin Xie 1 , Qi-Hua Zhao 1
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Four Zn(II) coordination polymers (CPs), namely, [Zn(3-bpdb)(MeO-ip)]n (1), [Zn(3-bpdb)(EtO-ip)]n (2), {[Zn(3-bpdb)(n-PrO-ip)]·H2O}n (3), and [Zn(3-bpdb)(n-BuO-ip)]n (4), have been first prepared under solvothermal conditions on the basis of four 5-substituted isophthalic acid ligands including 5-methoxy-1,3-benzenedicarboxylate (MeO-H2ip), 5-ethoxy-1,3-benzenedicarboxylate (EtO-H2ip), 5-propoxy-1,3-benzenedicarboxylate (n-PrO-H2ip), and 5-butoxy-1,3-benzenedicarboxylate (n-BuO-H2ip) with the help of 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpdb) as a secondary ligand. CPs 1 and 2 exhibit double pillared layered three-dimensional (3D) structures with non-interpenetrated fsc topology. CP 3 possesses a two-dimensional (2D) terrace layered structure with (42.6)(42.67.8) topology, while CP 4 features a one-dimensional (1D) infinite tubular helical chain. Second, when the orange-yellow crystals of 4 were immersed in the mother liquor at room temperature, vivid bright yellow crystals of {[Zn(3-bpdb)(n-BuO-ip)]·2H2O}n (5) with a 2D terrace layered structure and bright yellow crystals of {[Zn(3-bpdb)(n-BuO-ip)(H2O)]·1.5H2O}n (6) with a single-layered 2D (4,4) grid network were obtained on the 8th and 20th days by single-crystal-to-single-crystal (SCSC) phase transformation, respectively. These structural transformations were thoroughly studied by powder X-ray diffraction (PXRD) analysis and field-emission scanning electron microscopy (FE-SEM) along with single-crystal X-ray diffraction. In order to clarify the structure control factors in this series of CPs, similar reactions with 1–4 were continuously carried out, except that Zn(NO3)2·6H2O was replaced by Co(NO3)2·6H2O, and four Co(II)-based CPs formulated as [Co(3-bpdb)(MeO-ip)]n (7), [Co(3-bpdb)(EtO-ip)]n (8), {[Co(3-bpdb)(n-PrO-ip)]·H2O}n (9), and [Co(3-bpdb)(n-BuO-ip)]n (10) were purposefully constructed. The whole structures of 7–10 are isostructural with 1–3 and 5, respectively. The present results reveal that substitutions of isophthalic acid ligands with different lengths exert significant effects on the architecture of the CPs. Besides, the fluorescent properties of 1–6 were also investigated. The magnetic measurements indicate that CP 7 exhibits weak antiferromagnetic interactions, and CPs 8–10 exhibit weak ferromagnetic interactions within the binuclear (CoII)2 units. Magnetostructure relationships were investigated as well.
中文翻译：
R-取代基诱导的结构多样性和配位聚合物的单晶到单晶转变：合成、发光和磁性行为
四种Zn(II)配位聚合物(CP)，即[Zn(3-bpdb)(MeO-ip)] n ( 1 ), [Zn(3-bpdb)(EtO-ip)] n ( 2 ), { [Zn(3-bpdb)( n -PrO-ip)]·H 2 O} n ( 3 ) 和[Zn(3-bpdb)( n -BuO-ip)] n ( 4 )在溶剂热条件下，基于四种 5-取代的间苯二甲酸配体，包括 5-甲氧基-1,3-苯二甲酸酯 (MeO-H 2 ip)、5-乙氧基-1,3-苯二甲酸酯(EtO-H 2 ip)、5 -丙氧基-1,3-苯二甲酸酯( n -PrO-H 2ip) 和 5-丁氧基-1,3-苯二甲酸酯( n -BuO-H 2 ip) 在 1,4-双(3-吡啶基)-2,3-二氮杂-1,3-丁二烯 (3 -bpdb) 作为二级配体。CP 1和2表现出具有非互穿fsc拓扑结构的双柱层状三维 (3D) 结构。CP 3具有具有 (4 2 .6)(4 2 .6 7 .8) 拓扑结构的二维 (2D) 平台层状结构，而 CP 4具有一维 (1D) 无限管状螺旋链。二、当橙黄色结晶4在室温下浸入母液中，{[Zn(3-bpdb)( n -BuO-ip)]·2H 2 O} n ( 5 ) 的鲜艳亮黄色晶体具有二维梯级层状结构和亮黄色晶体{[Zn(3-bpdb)( n -BuO-ip)(H 2 O)]·1.5H 2 O} n ( 6) 具有单层 2D (4,4) 网格网络，分别在第 8 天和第 20 天通过单晶到单晶 (SCSC) 相变获得。这些结构转变通过粉末 X 射线衍射 (PXRD) 分析和场发射扫描电子显微镜 (FE-SEM) 以及单晶 X 射线衍射进行了彻底研究。为了与澄清在这一系列的CP，类似的反应的结构控制的因素1 - 4被连续地进行，不同之处在于锌（NO 3）2 ·6H 2 O的由钴（NO替换3）2 ·6H 2 ö , 和四个基于 Co(II) 的 CPs 公式化为 [Co(3-bpdb)(MeO-ip)] n( 7 ), [Co(3-bpdb)(EtO-ip)] n ( 8 ), {[Co(3-bpdb)( n -PrO-ip)]·H 2 O} n ( 9 ), [ Co(3-bpdb)( n -BuO-ip)] n ( 10 ) 是有目的地构建的。7 – 10的整个结构分别与1 – 3和5是同构的。目前的结果表明，不同长度的间苯二甲酸配体的取代对 CP 的结构产生了显着影响。此外，1 – 6的荧光特性也被调查了。磁性测量表明，CP 7个表现出弱的反铁磁相互作用，和CP 8 - 10显示出弱相互作用铁磁的双核（联合内II）2个单元。还研究了磁结构关系。
更新日期：2021-09-01
中文翻译：
R-取代基诱导的结构多样性和配位聚合物的单晶到单晶转变：合成、发光和磁性行为
四种Zn(II)配位聚合物(CP)，即[Zn(3-bpdb)(MeO-ip)] n ( 1 ), [Zn(3-bpdb)(EtO-ip)] n ( 2 ), { [Zn(3-bpdb)( n -PrO-ip)]·H 2 O} n ( 3 ) 和[Zn(3-bpdb)( n -BuO-ip)] n ( 4 )在溶剂热条件下，基于四种 5-取代的间苯二甲酸配体，包括 5-甲氧基-1,3-苯二甲酸酯 (MeO-H 2 ip)、5-乙氧基-1,3-苯二甲酸酯(EtO-H 2 ip)、5 -丙氧基-1,3-苯二甲酸酯( n -PrO-H 2ip) 和 5-丁氧基-1,3-苯二甲酸酯( n -BuO-H 2 ip) 在 1,4-双(3-吡啶基)-2,3-二氮杂-1,3-丁二烯 (3 -bpdb) 作为二级配体。CP 1和2表现出具有非互穿fsc拓扑结构的双柱层状三维 (3D) 结构。CP 3具有具有 (4 2 .6)(4 2 .6 7 .8) 拓扑结构的二维 (2D) 平台层状结构，而 CP 4具有一维 (1D) 无限管状螺旋链。二、当橙黄色结晶4在室温下浸入母液中，{[Zn(3-bpdb)( n -BuO-ip)]·2H 2 O} n ( 5 ) 的鲜艳亮黄色晶体具有二维梯级层状结构和亮黄色晶体{[Zn(3-bpdb)( n -BuO-ip)(H 2 O)]·1.5H 2 O} n ( 6) 具有单层 2D (4,4) 网格网络，分别在第 8 天和第 20 天通过单晶到单晶 (SCSC) 相变获得。这些结构转变通过粉末 X 射线衍射 (PXRD) 分析和场发射扫描电子显微镜 (FE-SEM) 以及单晶 X 射线衍射进行了彻底研究。为了与澄清在这一系列的CP，类似的反应的结构控制的因素1 - 4被连续地进行，不同之处在于锌（NO 3）2 ·6H 2 O的由钴（NO替换3）2 ·6H 2 ö , 和四个基于 Co(II) 的 CPs 公式化为 [Co(3-bpdb)(MeO-ip)] n( 7 ), [Co(3-bpdb)(EtO-ip)] n ( 8 ), {[Co(3-bpdb)( n -PrO-ip)]·H 2 O} n ( 9 ), [ Co(3-bpdb)( n -BuO-ip)] n ( 10 ) 是有目的地构建的。7 – 10的整个结构分别与1 – 3和5是同构的。目前的结果表明，不同长度的间苯二甲酸配体的取代对 CP 的结构产生了显着影响。此外，1 – 6的荧光特性也被调查了。磁性测量表明，CP 7个表现出弱的反铁磁相互作用，和CP 8 - 10显示出弱相互作用铁磁的双核（联合内II）2个单元。还研究了磁结构关系。
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