Unique Thermal Structural Phase Transitions Exhibited by Unsymmetrical Organometallic Gold(III)‐Dithiolene Complexes with Pentylthio and Hexylthio Groups
Unique Thermal Structural Phase Transitions Exhibited by Unsymmetrical Organometallic Gold(III)‐Dithiolene Complexes with Pentylthio and Hexylthio Groups
复制标题
具有戊硫基和己硫基的不对称有机金属金(III)-二硫醇烯配合物表现出独特的热结构相变
DOI：
10.1002/ejic.202300017
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发表时间：
2023
影响因子：
2.3
通讯作者：
Kubo Kazuya
中科院分区：
文献类型：
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作者：
Arata Sonomi;Kim Yuna;Hoshino Norihisa;Tahara Keishiro;Takahashi Kiyonori;Kadoya Tomofumi;Inoue Tomonori;Nakamura Takayoshi;Akutagawa Tomoyuki;Yamada Jun‐ichi;Kubo Kazuya
不对称金（III）-二硫杂环戊烯配合物是表现出热结构相变的分子材料的潜在候选者。在本研究中，合成了不对称的ppy-金（III）（ppy−=C-去质子化-2-苯基吡啶（−））配合物[AuC 5]和[AuC 6]，其由含有四硫富瓦烯（TTF）骨架的二硫烯配体配位，具有戊硫基（2-{双（戊硫基）-1，3-二硫醇-2-亚基}-1，3-二硫醇-4，5-二硫醇盐（2-））和己硫基（2-{双（己硫基）-1，3-二硫醇-2-亚基}-1，3-二硫醇-4，5-二硫醇盐（2-））。由于分子内配体-配体电荷转移，两种配合物在约508 nm处均表现出大的吸收带。在晶体中构建了具有围绕金属离子的首尾分子排列的一维柱状结构。柔性烷硫基插入到柱中二硫杂环戊烯配体之间的晶体空间中。[AuC 5]在198 °C时在结晶相和各向同性相之间表现出不可逆的简单相变。在25 °C下观察到的[AuC 6]结晶相在148 °C下熔化。另一种结晶相在148 °C以上以非常缓慢的结晶速率从液相生长，并在200 °C下完全转化为各向同性相。
Unsymmetrical gold(III)‐dithiolene complexes are potential candidates for molecular materials that exhibit thermal structural phase transitions. In this study, unsymmetrical ppy‐gold(III) (ppy−=C‐deprotonated‐2‐phenylpyridine(−)) complexes [AuC5] and [AuC6] coordinated by dithiolene ligands containing tetrathiafulvalene (TTF) skeletons with pentylthio (2‐{bis(pentylthio)‐1,3‐dithiol‐2‐ylidene}‐1,3‐dithiol‐4,5‐dithiolate(2−)) and hexylthio groups (2‐{bis(hexylthio)‐1,3‐dithiol‐2‐ylidene}‐1,3‐dithiol‐4,5‐dithiolate(2−)) were synthesized. Both complexes exhibited a large absorption band at approximately 508 nm, owing to intramolecular ligand‐to‐ligand charge transfer. One‐dimensional columnar structures with head‐to‐tail molecular arrangements around the metal ions were constructed in the crystals. The flexible alkylthio groups were intercalated into crystalline spaces between dithiolene ligands in the columns. [AuC5] exhibits a simple phase transition at 198 °C between crystalline and isotropic phases irreversibly. The crystalline phase of [AuC6] observed at 25 °C melted at 148 °C. Another crystalline phase grew above 148 °C with a very slow crystallization rate from the liquid phase and was completely transformed into an isotropic phase at 200 °C.