文档介绍：湘潭大学
硕士学位论文
卟啉镁配合物的合成、表征和性能及卟啉配合物晶体结构研究
姓名:曹华
申请学位级别:硕士
专业:有机化学
指导教师:赵鸿斌
20070501
摘要

卟啉类化合物具有特殊的结构和性能,在光电转化、仿生学、催化材料、气
体传感器、太阳能贮存、微量分析等领域有着重要的作用,卟啉化合物研究越来
越活跃。
本文合成了未见文献报道的的 meso-四(对烷氧基苯基)卟啉镁配合物 10 个。
用 UV-vis, 1H NMR,IR,MS 和元素分析对其结构进行了表征和确证。
用差示扫描量热法(DSC)和偏光显微镜(PM)对所合成的 10 个配合物的
液晶性质进行了研究。结果表明,其中 6 个配合物具有液晶性质,有 1~3 个中
介相,有确定的相转变温度、热焓△H 和相变区间。液晶相起始温度最高为
℃,最低为 ℃。液晶相变区间△T 最宽为 ℃,△T 最窄 ℃。通
过 PM 观察该系列化合物液晶态为丝状织构。它们的液晶行为表现为升温单变液
晶。
通过蒸气扩散法得到了 meso-四(对正戊烷氧基苯基)卟啉及其 Ag, Zn, Ni 配
合物四个单晶,用 X-ray 单晶衍射对它们的晶体结构进行了分析。结果表明,
meso-四(对正戊烷氧基苯基)卟啉及其 Ag, Zn 配合物的卟啉环高度共平面,而 Ni
配合物的卟啉环扭曲成马鞍状。分子间 C-H…π作用力使分子首尾相连形成环状
结构。
本文还对 3 个六氢吡啶二硫代氨基甲酸衍生物的晶体结构进行了分析,在这
3 个化合物中,六氢吡啶环均为椅式结构,晶体结构中存在分子间氢键和π-π堆
积作用。

关键词:卟啉镁配合物;合成;表征;液晶;晶体结构

Ⅰ
ABSTRACT

As the particular structure and the nature of the porphyrins, they are importance
in the field of photoelectronic conversion, biomimetic, catalytic materials, gas
sensor, solar storage, microanalysis, etc. Today, the research on porphyrin derivation
is more and more active.
A series of plexes of meso-tetrakis(4-alkoxyphenyl)porphyrin
were synthesized in this paper, their molecular structures were characterized by
UV-vis, 1H NMR, IR, MS and elemental analysis.
Differential scanning calorimetry (DSC) and polarizing microscope (PM) were
used to study the liquid properties of the pounds. Among them, there were
Six found to exhibit liquid crystal (.)properties, they had one to three
mesophases and certain phase transition temperature, ΔH and temperature range of
.(ΔT). The highest initial temperature of phase transition was ℃, the
lowest ℃. The widest temperature of phase transiton was ℃ and the
narrowest ℃. The liuquid crystalline state displayed as filamentary texture
observed by PM. All them displayed as heating monotropic liquid crystals.
The single crystals of meso-tetrakis(4-alkoxyphenyl)por