Discotic liquid crystals of transition metal complexes 45: parity effect of the number of d-electrons on stacking distances in the columnar mesophases of octakis-(m-alkoxyphenoxy)phthalocyaninato metal(II) complexes
Discotic liquid crystals of transition metal complexes 45: parity effect of the number of d-electrons on stacking distances in the columnar mesophases of octakis-(m-alkoxyphenoxy)phthalocyaninato metal(II) complexes
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过渡金属配合物45的盘状液晶：d电子数对八(间烷氧基苯氧基)酞菁金属(II)配合物柱状中间相堆积距离的宇称效应
DOI：
10.1142/s1088424612501131
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发表时间：
2012
影响因子：
1.5
通讯作者：
Hiroyuki Sato
中科院分区：
文献类型：
--
作者：
Kentaro Kawai;Junichi Uchikoshi;Kenta Arima;and Mizuho Morita;Hiroyuki Sato
我们合成了34种新型同系盘状液晶，八(间烷氧基苯氧基)酞菁金属(II){缩写为(m-CnOPhO)8PcM (M = Co(1), Ni(2), Cu(3), Zn(4) and H2(5); n = 8(a), 10(b), 12(c), 14(d), 16（e），18（f）和20（g））}，并研究了d电子数量对其柱状中间相堆积距离的宇称效应。温度依赖性广角 X 射线衍射研究表明，钴(II) (d7) 配合物 (1a–1g) 和铜(II) (d9) 配合物 (3b–3g) 均显示出单个六方有序柱状 (Colho) 中间相，堆积距离非常短，为 3.3 Å，而镍(II) (d8) 配合物 (2a–2g) 和不含金属的(d0) 衍生物 (5a–5g) 显示出单个伪六方有序柱状 (Colrho) 中间相，堆积距离稍长，为 3.4 Å。非常有趣的是，镍配合物（2a）和无金属衍生物（5a-5c）给出了一个非常大的（001）反射峰和第二个（002）反射峰。此外，锌（II）（d10）配合物（4a-4g）显示出两种不同的矩形有序柱状中间相，Colro（P2/m）和Colro（P21/a），堆积距离稍长，为3.4 Å。因此，奇数个 d 电子出现较短的堆积距离 3.3 Å，而偶数个 d 电子出现较长的堆积距离 3.4 Å。因此，堆叠距离取决于中心金属（II）中 d 电子数量的奇偶性。据我们所知，这是宇称效应对柱状中间相堆积距离的第一个例子。
We have synthesized 34 novel homologous discotic liquid crystals, octakis(m-alkoxyphenoxy)phthalocyaninato metal(II) {abbreviated as (m-CnOPhO)8PcM (M = Co(1), Ni(2), Cu(3), Zn(4) and H2(5); n = 8(a), 10(b), 12(c), 14(d), 16(e), 18(f) and 20(g))}, and investigated parity effect of the number of d-electrons on the stacking distances in their columnar mesophases. It was revealed from temperature-dependent wide angle X-ray diffraction studies that each of the cobalt(II) (d7) complexes (1a–1g) and the copper(II) (d9) complexes (3b–3g) showed a single hexagonal ordered columnar (Colho) mesophase with a very short stacking distance at 3.3 Å, and that the nickel(II) (d8) complexes (2a–2g) and the metal-free (d0) derivatives (5a–5g) showed a single pseudo-hexagonal ordered columnar (Colrho) mesophase with a little bit longer stacking distances at 3.4 Å. Very interestingly, the nickel complex (2a) and metal-free derivatives (5a–5c) gave an extremely big (001) reflection peak with the second (002) reflection peak. Furthermore, the zinc(II) (d10) complexes (4a–4g) showed two different rectangular ordered columnar mesophases, Colro(P2/m) and Colro(P21/a), with a little bit longer stacking distance at 3.4 Å. Thus, the shorter stacking distance, 3.3 Å, appeared for the odd number of d-electrons, whereas the longer stacking distance, 3.4 Å, appeared for the even number of d-electrons. Hence, the stacking distances depend on parity of the number of d-electrons in the central metal(II). To our best knowledge, it is the first example of parity effect on the stacking distances in columnar mesophases.