Cooperative phenomenon of vapochromism and proton conduction of luminescent Pt(II) complexes for the visualisation of proton conductivity,Faraday Discussions

当前位置： X-MOL 学术 › Faraday Discuss. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Cooperative phenomenon of vapochromism and proton conduction of luminescent Pt(II) complexes for the visualisation of proton conductivity
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-4-14 , DOI: 10.1039/d0fd00001a
Atsushi Kobayashi _{1,

2,

3,

4,

5} , Shin-ichiro Imada _{1,

2,

3,

4,

5} , Dongjin Wang _{5,

6,

7,

8} , Yuki Nagao _{5,

6,

7,

8} , Masaki Yoshida _{1,

2,

3,

4,

5} , Masako Kato _{1,

2,

3,

4,

5}

Affiliation

The luminescent and proton conductive Pt(II) complex [PtCl(tpy-o-py)]Cl and its HCl adduct [PtCl(tpy-o-pyH)]Cl₂ (o-Pt and o-Pt·HCl, respectively; tpy-o-py = 2,2′:6′,2′′-terpyridine-6′,2′′′-pyridine) were synthesised and their crystal structures, vapochromic behaviour, and proton conduction, were investigated and compared to those of the para isomers [PtCl(tpy-p-py)]Cl and [PtCl(tpy-p-pyH)]Cl₂ (p-Pt and p-Pt·HCl, respectively; tpy-p-py = 2,2′:6′,2′′-terpyridine-4′,4′′′-pyridine). X-ray structure analysis revealed that the intermolecular metallophilic (Pt⋯Pt) interaction was negligible in o-Pt but effective in o-Pt·HCl. Reversible transformation between o-Pt and o-Pt·HCl coupled with significant colour and luminescence changes was achieved by four different external stimuli, namely: exposure of o-Pt to humid HCl gas to form o-Pt·HCl, heating, exposure to MeOH vapour, and finally drying in air to regenerate the original o-Pt. The intraligand π–π* orange emission observed for o-Pt exhibited negligible dependence on the relative humidity (RH). Conversely, o-Pt·HCl exhibited red metal–metal-to-ligand charge-transfer (MMLCT) phosphorescence at 725 nm, originating from effective intermolecular Pt–Pt interactions, and interesting vapochromic behaviour that was dependent on the RH. Notably, o-Pt·HCl presented higher conductivity than the p-Pt·HCl isomer at RH < 80%. This trend was reversed at RH values > 80%, probably owing to the second water-adsorption-induced transformation of p-Pt·HCl. The cooperative phenomenon between the proton conduction and vapochromic behaviour observed for both o-Pt·HCl and p-Pt·HCl should allow the visualisation of the proton-conducting pathway, without the need for a bulk electrode, via the absorption and emission colours at both macroscopic and microscopic levels.

中文翻译：

可视化质子电导率的发光Pt（II）配合物的变色与质子传导的合作现象

发光和质子传导性Pt（II）配合物[PtCl（tpy- o- py ）] Cl及其HCl加合物[PtCl（tpy- o- pyH）] Cl ₂（分别为o- Pt和o- Pt·HCl；合成了tpy- o -py = 2,2'：6'，2''-terpyridine-6'，2'''-pyridine）并研究了它们的晶体结构，蒸气致变色行为和质子传导对位异构体[PtCl（tpy- p -py ）] Cl和[PtCl（tpy- p -pyH）] Cl _2的合成（分别为p -Pt和p -Pt·HCl； tpy- p-py = 2,2'：6'，2''-叔吡啶-4'，4'''-吡啶）。X射线结构分析表明，分子间的金属间（Pt⋯Pt）相互作用在邻-Pt中可忽略不计，但在邻-Pt·HCl中有效。o -Pt和o -Pt·HCl之间的可逆转化以及显着的颜色和发光变化是通过四种不同的外部刺激实现的，即：o -Pt暴露于潮湿的HCl气体中形成o -Pt·HCl，加热， MeOH蒸气，最后在空气中干燥以再生原始的o -Pt。o观察到的配体内π–π *橙色发射-Pt对相对湿度（RH）的依赖性可忽略不计。相反，邻-Pt·HCl在725 nm处显示红色金属-金属-配体电荷转移（MMLCT）磷光，源于有效的分子间Pt-Pt相互作用，以及取决于RH的有趣的变色行为。值得注意的是，在RH <80％时，o -Pt·HCl的电导率高于对-Pt·HCl的异构体。在RH值> 80％时，这种趋势被逆转了，这可能是由于第二次水吸附引起的对-Pt·HCl的转化。o -Pt·HCl和O- Pt·HCl的质子传导和气相致变色行为之间的协同现象p- Pt·HCl可以通过宏观和微观水平的吸收和发射颜色，使质子传导途径可视化，而不需要大体积电极。

更新日期：2020-04-14

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11