两个蒽基Au(Ⅰ)配合物[Au(anbdtim)2]PF6和[Au(anbdtim)2][Au(CN)2]的结构调控和发光转换
Two anthracene-based Au(Ⅰ) complexes [Au(anbdtim)2]PF6 and [Au(anbdtim)2][Au(CN)2]: Structural modulation and luminescence switching
作者单位E-mail
黄建工 南京大学化学化工学院, 南京 210093  
万复舜 南京大学化学化工学院, 南京 210093  
叶程辉 南京大学化学化工学院, 南京 210093  
陈文文 南京大学化学化工学院, 南京 210093  
吕欣彤 南京大学化学化工学院, 南京 210093  
曹登科 南京大学化学化工学院, 南京 210093 dkcao@nju.edu.cn 
摘要: 合成了2个蒽基配合物[Au (anbdtim)2]PF6(1)和[Au (anbdtim)2][Au (CN)2](2),其中anbdtim=2-蒽基-4,5-双(2,5-二甲基(3-噻吩基))-1-甲基咪唑。它们含有不同的抗衡阴离子,1中的为PF6-,2中的为[Au (CN)2]-。这导致2个配合物在溶液和固态中都表现出显著不同的荧光。在CH2Cl2溶液中,配合物12的荧光发射波长分别为465和445 nm。在固态,12的荧光发射波长分别为450和478 nm。有趣的是,配合物2对苯分子很敏感,它在苯中的荧光发射波长为475 nm (量子产率Φ=66.5%),在CH2Cl2中为448 nm (Φ=22.9%)。此外,我们利用配合物2的苯溶液蒸发制备了蓝绿色发光固体2-benzene。当交替地除去和再次加入苯,固体2-benzene的荧光发射在蓝绿色(491 nm)和钢蓝色(460 nm)之间可逆地转换。在实验结果的基础上,我们讨论了抗衡阴离子和苯分子对12的发光行为的影响。
关键词:   Au(Ⅰ)配合物  亲金作用  结构调控  发光转换
基金项目: 国家自然科学基金(No.21871134)资助。
Abstract: Two anthracene-based complexes[Au(anbdtim)2]PF6 (1) and[Au(anbdtim)2] [Au(CN)2] (2) have been synthesized, where anbdtim=2-(anthracenyl)-4,5-bis(2,5-dimethyl(3-thienyl))-1-methyl-imidazole. The different counter anions, PF6- in 1 and[Au(CN)2]- in 2, led to significantly different fluorescence between 1 and 2 both in solution and in the solid state. Complexes 1 and 2 in CH2Cl2revealed an emission at 465 and 445 nm, respectively, and their solidstate luminescence exhibited an emission at 450 nm for 1 and 478 nm for 2. Interestingly, the luminescence of 2 was sensitive to benzene molecules, with an emission at 475 nm (quantum yield Φ=66.5%) in benzene while 448 nm (Φ=22.9%) in CH2Cl2. Moreover, the blue-green-emitting solid 2-benzene was prepared by the evaporation of a benzene solution of complex 2. This solid exhibited reversible luminescence switching between blue-green emission at 491 nm and steel-blue emission at 460 nm upon alternately removing and incorporating benzene molecules. On the basis of these experimental results, we discussed the influence of counter anions and benzene molecules on the luminescence behaviours of 1 and 2.
Keywords: anthracene  Au(Ⅰ) complex  aurophilicity  structural modulation  luminescence switching
投稿时间:2022-11-30 修订日期:2023-03-17
摘要点击次数:  1303
全文下载次数:  596
黄建工,万复舜,叶程辉,陈文文,吕欣彤,曹登科.两个蒽基Au(Ⅰ)配合物[Au(anbdtim)2]PF6和[Au(anbdtim)2][Au(CN)2]的结构调控和发光转换[J].无机化学学报,2023,39(5):959-966.
查看全文  查看/发表评论  下载PDF阅读器
Support information: 相关附件:   220522_SI_of_anthracene-based_Au(I)_complexes_R1.docx