The engineering of stilbazolium/iodocuprate hybrids with optical/electrical performances by modulating inter-molecular charge transfer among H-aggregated chromophores,Inorganic Chemistry Frontiers

当前位置： X-MOL 学术 › Inorg. Chem. Front. › 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.)

The engineering of stilbazolium/iodocuprate hybrids with optical/electrical performances by modulating inter-molecular charge transfer among H-aggregated chromophores
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020/02/10 , DOI: 10.1039/c9qi01672d
Wei Wu _{1,

2,

3,

4} , Xiang-Ling Lin _{1,

2,

3,

4} , Qian Liu _{1,

2,

3,

4} , Yan He _{1,

2,

3,

4} , You-Ren Huang _{1,

2,

3,

4} , Bin Chen _{1,

2,

3,

4} , Hao-Hong Li _{1,

2,

3,

4} , Zhi-Rong Chen _{1,

2,

3,

4}

Affiliation

The combination of D–π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids, these were, [(CMAMP)₂(CuI₃)(acetone)_0.5]_n (1), [(HMAMP)(Cu₃I₄)]_n (2), and [(HMAHP)₂(Cu₅I₇)]_n (3), which present natural quantum-well architectures with void spaces of quasi-2-D organic layers occupied by iodocuprate anions via C–H⋯I hydrogen bonds. The D–π-A stilbazolium dyes exhibit head-to-tail arranged H-aggregations with face-to-face π⋯π stacking interactions. Theoretical calculations suggest that the charge densities on the benzenes can be strengthened from the electron-withdrawing group (–CN) to the electron-donating group (–OH), and the –C₂H₅OH substituents on the ortho-N of the pyridines not only help to open up the band gaps, but also provide a steric effect for better face-to-face π⋯π stacking interactions. Therefore, HMAHP⁺ in 3 possesses the strongest face-to-face π⋯π stacking interactions owing to the presence of a longer –C₂H₅OH group in the ortho-N position, and consequently, blue-shifted photoluminescence, a stronger photocurrent (0.28 mA), and a higher ON/OFF ratio (1.6 × 10⁴) can be observed in 3. In particular, electrical bistability performances can be observed in ITO/hybrids/poly (methyl methacrylate) (PMMA)/Ag devices, which are explained using Schottky emission, space-charge-limited current effect (SCLC) and Ohmic mechanisms. According to theoretical calculations, the band gap switching from the semi-conductor to the conductor (high resistance state (HRS) to low resistance state (LRS)) after trapping electrons is exclusively dominated by the π bonding and anti-bonding orbitals of the stilbazolium dyes, which indicates a future direction for the design of stilbazolium-containing memory devices.

中文翻译：

通过调节H聚集的生色团之间的分子间电荷转移来设计具有光/电性能的stilbazolium / iodocuprate杂化体

带有邻N-烷基取代基的D–π-A噻唑类发色团与碘多普酸盐的结合产生了三种新型杂种，它们是[（CMAMP）₂（CuI ₃）（丙酮）_0.5 ] _n（1），[ （HMAMP）（Cu ₃ I ₄）] _n（2）和[（HMAHP）₂（Cu ₅ I ₇）] _n（3），它们呈现出具有准2- D有机空隙的天然量子阱结构通过iodocuprate阴离子占据的层通过C–H⋯I氢键。D-π-Astilbazolium染料具有从头到尾排列的H聚集体，且具有面对面的π⋯π堆积相互作用。理论计算表明，从吸电子基团（-CN）到给电子基团（-OH）可以增强苯上的电荷密度，并且邻位-N上的-C ₂ H ₅ OH取代基可以增强。吡啶不仅有助于打开带隙，而且还提供空间位阻效应，以实现更好的面对面π⋯π堆叠相互作用。因此，HMAHP ⁺在3具有最强的面到面π⋯π堆叠由于较长-C存在相互作用₂ ħ ₅ OH基团在邻位-N位置，因此，在3中可以观察到蓝移的光致发光，更强的光电流（0.28 mA）和更高的开/关比（1.6×10 ⁴）。尤其是，可以在ITO /混合材料/聚（甲基丙烯酸甲酯）（PMMA）/ Ag器件中观察到电双稳态性能，这可以使用肖特基发射，空间电荷限制电流效应（SCLC）和欧姆机制进行解释。根据理论计算，俘获电子后从半导体到导体的带隙切换（高阻态（HRS）到低阻态（LRS））仅由the的π键和反键轨道控制染料，这指示了含有stilbazolium的存储设备设计的未来方向。

更新日期：2020-03-19

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