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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Modulating the regioselectivity of solid-state photodimerization in coordination polymer crystals
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Modulating the regioselectivity of solid-state photodimerization in coordination polymer crystals

机译：调制固态光二聚体化在配位聚合物晶体中的区域选择性

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Coordination polymers [Cd(1,4-bpeb)(L-1)] (1), [Zn-2(1,4-bpeb)(2)(L-2)(2)(SO42-)(2)] (2) and [Cd(1,4-bpeb)(L-3)] (H2O) (3) (H2L1, 3-[2-(3-hydroxy-phenoxymethyl)-benzyloxy]-benzoic acid; HL2, 1H-Indazole-3-carboxylic acid; H3L3, benzene-1,2,3-tricarboxylic acid; 1,4-bpeb, 1,4-bis[2-(4-pyridyl)vinyl]benzene have been synthesized under solvothermal conditions. Complexes1-3 underwent photodimerization in the solid-state to give quantitative yields of single isomeric products. The choice of carboxyl ligands L and metal center determined the arrangement of 1,4-bpeb ligands, which in turn directed the regiochemistry of the final photoproducts. The solid-state network structures of cadmium based 1 and 3 had 1,4-bpeb pairs aligned face-to-face with both C = C centres in each ligand at an appropriate distance and alignment for photodimerization to give the correspondingpara-[2.2]cyclophane (pCP) exclusively. By contrast, compound2possessed dinuclear (ZnSO4)(2)metallocycles that positioned the 1,4-bpeb "arms" face-to-face, but with C = C centres offset at an appropriate distance for only one pair to undergo [2 + 2] cyclo-addition to yield a single stereoisomer of the monocyclobutane photo-product bpbpvpcb. This work highlights crystal engineering design principles that can be used to facilitate regio- and stereospecificity in solid-state transformations.
机译：配位聚合物[Cd（1,4-BPEB）（1）]（1），[Zn-2（1,4-BPEB）（2）（2）（2）（2）（SO 42 - ）（2） ]（2）和[CD（1,4- BPEB）（L-3）]（H 2 O）（3）（H2L1，3- [2-（3-羟基 - 苯氧基甲基） - 苄氧基] - 苯甲酸; HL2， -1H-吲唑-3-羧酸; H3L3，苯-1,2,3-三羧酸; 1,4- BPEB，1,4-双[2-（4-吡啶基）乙烯基]苯已被溶剂热条件下合成。复合物1-3在固态中进行光电二聚体，得到单一异构产物的定量产率。羧基配体L和金属中心的选择确定了1,4-BPEB配体的布置，这反过来指导了最终光调节的调节率。基于镉的1和3的固态网络结构具有1,4-BPEB对与每个配体中的C = C中心对齐，在适当的距离和对准的光电二聚体上以给予相应的para-[2.2 ]己烷（PCP）专门。相比之下，化合物2Possessed硫赤核（ZnSO 4）（2）定位为1的金属克， 4- BPEB“臂”面 - 面，但与C = C中心以适当的距离偏移量仅一对经历[2 + 2]环加成，得到monocyclobutane光产物bpbpvpcb的单一立体异构体。这项工作突出了水晶工程设计原理，可用于促进固态变换中的序列和立体性结构。

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    Hu Fei-Long; Qin Zhen; Wang Meng-Fan; Kang Xue Wan; Qin Yong-Li; Wang Yong; Chen Shu-Li; Young David James; Mi Yan;

  • 作者单位

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

    Charles Darwin Univ Coll Engn IT &

    Environm Darwin NT 0909 Australia;

    Guangxi Univ Nationalities Guangxi Key Lab Chem &

    Engn Forest Prod Nanning 530006 Peoples R China;

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  • 中图分类 化学;无机化学;
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