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首页> 外文期刊>Crystal growth & design >N-Donor-Functionalized Acetylacetones for Heterobimetallic Coordination Polymers, the Next Episode: Trimethylpyrazoles
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N-Donor-Functionalized Acetylacetones for Heterobimetallic Coordination Polymers, the Next Episode: Trimethylpyrazoles

机译：N-供体官能化乙酰丙酮用于异常配位聚合物，下一集：三甲基吡唑

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摘要

The ditopic molecule 3-(1,3,5-trimethyl-4-1H-pyrazolyl)acetylacetone (HacacMePz) combines an acetylacetone group suitable for deprotonation and O,O' coordination to a Pearson hard cation with a softer N-donor site. Both binding modes were employed individually: the pyrazolyl moiety was coordinated to Zn-II, Hg-II, and Ag-I, and with trivalent iron the tris-chelating O,O' complex [Fe(acacMePz)(3)] was isolated. The Cu-II derivative shows shorter O,O' chelation and N coordination in the more distant Jahn-Teller sites and exists in two alternative crystal forms: namely, as a tetranuclear discrete complex and as a chain polymer. The different Pearson hardnesses of the coordination sites of acacMePz(-) allow for the design of well-ordered mixed-metal solids. Selective complexation to a hard and soft cations was achieved in coordination polymers combining hard Fe-III and softer Hg-II or Ag-I. Even slight differences in Pearson hardness based on different oxidation states of the same cation imply sufficient selectivity, as shown by the successful synthesis of a mixed-valence Cu-II/Cu-I chain polymer. A synopsis of all structurally characterized compounds confirms that HacacMePz represents a bridging ligand with restricted conformational freedom. No full rotation about the single bond between the pyrazolyl and acetylacetone fragments occurs, and dihedral angles between these moieties are limited to values of 90 +/- 17 degrees.
机译：双视性分子3-（1,3,5-三甲基-4-1H-吡唑基）乙酰丙酮（HacacMePz）结合了一个适合脱质子的乙酰丙酮基团，并与皮尔逊硬阳离子的O，O'配位，以及一个更软的N-施主位置。分别采用两种结合模式：吡唑基部分与Zn II、Hg II和Ag-I配位，并与三价铁分离出三价铁螯合O，O'络合物[Fe（acacMePz）（3）]。Cu II衍生物在较远的Jahn-Teller位点显示出较短的O，O'螯合和N配位，并以两种可选的晶体形式存在：即作为四核离散络合物和链聚合物。acacMePz（-）配位点的不同皮尔逊硬度允许设计有序的混合金属固体。在结合硬Fe III和软Hg II或Ag-I的配位聚合物中，实现了对硬阳离子和软阳离子的选择性络合。根据同一阳离子的不同氧化状态，皮尔逊硬度即使略有差异，也意味着足够的选择性，成功合成了混合价态Cu II/Cu-I链聚合物就表明了这一点。对所有结构特征化合物的概述证实，HacacMePz代表一种构象自由受限的桥配体。吡唑基和乙酰丙酮片段之间的单键没有完全旋转，这些部分之间的二面角限制在90+/-17度。

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  • 来源
    《Crystal growth & design》 |2021年第5期|共8页
  • 作者

    van Terwingen Steven; Nachtigall Noah; Ebel Ben; Englert Ulli;

  • 作者单位

    Rhein Westfal TH Aachen Inst Inorgan Chem D-52074 Aachen Germany;

    Rhein Westfal TH Aachen Inst Inorgan Chem D-52074 Aachen Germany;

    Rhein Westfal TH Aachen Inst Inorgan Chem D-52074 Aachen Germany;

    Rhein Westfal TH Aachen Inst Inorgan Chem D-52074 Aachen Germany;

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  • 正文语种 eng
  • 中图分类 晶体学;
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