Redox-triggered reversible modulation of intense near-infrared and visible absorption using a paddlewheel-type diruthenium(<scp>iii</scp>) complex
Redox-triggered reversible modulation of intense near-infrared and visible absorption using a paddlewheel-type diruthenium(<scp>iii</scp>) complex
复制标题
使用叶轮型二钌(<scp>iii</scp>)络合物进行氧化还原触发的强近红外和可见光吸收的可逆调制
DOI：
10.1039/d1dt01681d
复制
发表时间：
2021
影响因子：
4
通讯作者：
Handa Makoto
中科院分区：
文献类型：
--
作者：
Kataoka Yusuke;Imasaki Nanako;Yano Natsumi;Mitsumi Minoru;Handa Makoto
合成了一种新的2-氨基-3-(三氟甲基)吡啶(Amtfmp)[Ru2(Amtfmp)4Cl2]([1])的桨轮型二Ru配合物，具有较强的近红外(NIR)和可见光吸收，并通过单晶X射线衍射(SCXRD)对其结构进行了表征。由于其特征的配体-金属电荷转移和d-d吸收带在外部电压或化学试剂如十甲基钴(CoCp*2)的响应下发生开关切换，该配合物表现出可逆和戏剧性的近红外和可见电致变色行为，从深蓝色([1])到粉红色([1]−)。成功地分离了[1]的单电子还原物种，即[CoCp*2][1]，并通过SCXRD、磁化率与温度的关系和质谱学对其进行了全面的表征，证明了这种电致变色行为并没有对[1]进行显著的结构重组。
A new paddlewheel-type diruthenium complex with 2-amino-3-(trifluoromethyl)pyridine (amtfmp) [Ru2(amtfmp)4Cl2] ([1]), which shows intense and characteristic near-infrared (NIR) and visible absorption, has been developed and structurally characterized by single crystal X-ray diffraction (SCXRD) analyses. This complex exhibits reversible and dramatic NIR and visible electrochromic behavior from deep-blue ([1]) to pink ([1]−) due to the ON–OFF switching of its characteristic ligand-to-metal charge transfer (LMCT) and d–d absorption bands in response to an external voltage or chemical reagent such as decamethylcobaltocene (CoCp*2). The one-electron reduced species of [1], i.e., [CoCp*2][1], was successfully isolated and fully characterized via SCXRD, the temperature dependence of the magnetic susceptibility, and mass spectroscopy, proving that this electrochromic behavior occurs without significant structural reorganization of [1].