Synthesis, X-ray structures and NIR chiroptical properties of a series of dinuclear lanthanide(III) complexes [Ln_2{μ-(S- or RS-pba)}_4(HBpz_3)_2]; novel configurational chirality due to non-bonding Ln … O interactions

Md. Abdus Subhan; Takayoshi Suzuki; Akira Fuyuhiro; Sumio Kaizaki

首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, X-ray structures and NIR chiroptical properties of a series of dinuclear lanthanide(III) complexes [Ln_2{μ-(S- or RS-pba)}_4(HBpz_3)_2]; novel configurational chirality due to non-bonding Ln … O interactions

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Synthesis, X-ray structures and NIR chiroptical properties of a series of dinuclear lanthanide(III) complexes [Ln_2{μ-(S- or RS-pba)}_4(HBpz_3)_2]; novel configurational chirality due to non-bonding Ln … O interactions

机译：一系列双核镧系元素[Ln_2 {μ-（S-或RS-pba）} _ 4（HBpz_3）_2]的合成，X射线结构和近红外光谱特性。非键Ln…O相互作用引起的新型构型手性

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Two series of mononuclear [Ln~(III)(S- or RS-pba)(HBpz_3)_2](Ln = Tm, Er, Ho) and dinuclear [Ln_2{μ-(S- or RS-pba)}_4(HBpz_3)_2](Ln = Yb, Ho, Gd, Dy, Nd) complexes (pba = RS- and/or S-2-phenyl butyrate, HBpz_3 = hydrotris(pyrazoll-yl)borate) were prepared and their X-ray structures and NIR chiroptical properties investigated. Synthesis with a molar ratio 1:2:1 of Ln: KHBpz_3:pba results in the formation of either mono- or dinuclear complexes, depending on the Ln(III) ionic radii: mononuclear complex from Yb(III) to Ho(III) and dinuclear ones from Dy(III) to Nd(III). Only the dinuclear complexes for all of the Ln(III) studied were formed with a molar ratio 1:1:2 of Ln:KHBpz_3:pba. X-Ray structural analysis confirmed dinuclear structures with CH …π interactions and linear B … Ln … Ln … B arrangements for the Ln(μ-RS-pba)_4Ln(HBpz_3)_2(Yb, Ho, Dy, Gd and Nd) complexes and a skew bent arrangement of B … Ln … Ln … B leading to configurational chirality in the Dy(μ-S-pba)_4Dy(HBpz_3)_2 complex. Comparison of NIR chiroptical spectra in the 4f-4f transitions with those of the corresponding Cr-Ln complexes, [(acac)_2Cr(ox)Ln(HBpz_3)_2] suggests that the 4f-4f CD intensities arise from configurational chirality, probably due to the skew bent B … Ln … Ln … B disposition.

机译：两个系列的单核[Ln〜（III）（S-或RS-pba）（HBpz_3）_2]（Ln = Tm，Er，Ho）和双核[Ln_2 {μ-（S-或RS-pba）} _ 4（制备HBpz_3）_2]（Ln = Yb，Ho，Gd，Dy，Nd）配合物（pba =丁酸RS-和/或S-2-苯基丁酸酯，HBpz_3 =氢三（吡唑基）硼酸酯）并对其X射线进行分析的结构和近红外手性研究。 Ln：KHBpz_3：pba摩尔比为1：2：1的合成导致形成单核或双核配合物，具体取决于从Yb（III）到Ho（III）的Ln（III）离子半径：单核配合物从Dy（III）到Nd（III）的双核原子。仅以Ln：KHBpz_3：pba的摩尔比为1：1：2形成了所有研究的Ln（III）的双核配合物。 X射线结构分析证实了Ln（μ-RS-pba）_4Ln（HBpz_3）_2（Yb，Ho，Dy，Gd和Nd）络合物具有CH…π相互作用和线性B…Ln…Ln…B排列的双核结构和B…Ln…Ln…B的倾斜弯曲排列导致Dy（μ-S-pba）_4Dy（HBpz_3）_2配合物中的构型手性。比较4f-4f跃迁与相应Cr-Ln络合物[（acac）_2Cr（ox）Ln（HBpz_3）_2]的NIR手性光谱，表明4f-4f CD强度源自构型手性，可能是由于倾斜B…Ln…Ln…B的配置。

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《Dalton transactions: An international journal of inorganic chemistry》 |2003年第19期|共7页
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Md. Abdus Subhan; Takayoshi Suzuki; Akira Fuyuhiro; Sumio Kaizaki;
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1. Synthesis, X-ray structures and NIR chiroptical properties of a series of dinuclear lanthanide(III) complexes [Ln_2{μ-(S- or RS-pba)}_4(HBpz_3)_2]; novel configurational chirality due to non-bonding Ln … O interactions [J] . Md. Abdus Subhan, Takayoshi Suzuki, Akira Fuyuhiro, Dalton transactions: An international journal of inorganic chemistry . 2003,第19期

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Synthesis, X-ray structures and NIR chiroptical properties of a series of dinuclear lanthanide(III) complexes [Ln_2{μ-(S- or RS-pba)}_4(HBpz_3)_2]; novel configurational chirality due to non-bonding Ln … O interactions

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