Band gap engineering in pyridyl-functionalized two-dimensional (2D) CuSCN coordination polymers†

IF 3.2 3区 工程技术 Q2 CHEMISTRY, PHYSICAL
Jetnipat Songkerdthong, Thanasee Thanasarnsurapong, Adisak Boonchun, David J. Harding and Pichaya Pattanasattayavong
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Abstract

Copper(I) thiocyanate (CuSCN) has emerged as an excellent hole-transporting semiconductor with applications spanning across electronic and optoelectronic fields. The coordination chemistry of CuSCN allows for extensive structural versatility via ligand modification. In particular, CuSCN modified with pyridine (Py) derivatives can produce novel two-dimensional (2D) structures of the Cu–SCN network while also allowing for the tuning of electronic properties by changing the substituent group on Py. However, obtaining phase-pure 2D structures remains a challenge as the conventional method often yields mixed products of varying stoichiometry having different structures. In this work, we have developed a synthetic method that reliably produces phase pure [Cu(SCN)(3-XPy)]n complexes (X = OMe, H, Br, and Cl) in a 1 : 1 : 1 ratio all with confirmed 2D structures. The single crystal structure of [Cu(SCN)(3-OMePy)]n is also reported herein and compared with the reported structures of the other three compounds. Complexes with X = OMe and H show similar structures, in which the 2D layers are analogous to the buckled 2D sheets of silicene or blue phosphorene. On the other hand, for complexes with X = Br and Cl, their rippled 2D structures resemble the puckered 2D sheets found in black phosphorene. The variation of the electron-withdrawing ability of the substituent group is found to systematically shift the electronic energy levels and band gaps of the complexes, allowing the 2D CuSCN-based materials to display optical absorptions and emissions in the visible range. In addition, first-principles calculations reveal that the drastic change in the electronic levels is a result of the emergence of the Py ligand electronic states below the SCN states. This work demonstrates that the structural, electronic, and optical properties of 2D Cu–SCN networks can be systematically tailored through ligand modification.

Abstract Image

吡啶官能化二维 (2D) CuSCN 配位聚合物的带隙工程
硫氰酸铜(I)(CuSCN)已成为一种优秀的空穴传输半导体,其应用领域横跨电子和光电领域。CuSCN 的配位化学性质允许通过配体修饰实现广泛的结构多样性。在这项工作中,我们开发了一种合成方法,能以 1:1:1 的比例可靠地生产出相纯的 [Cu(SCN)(3-XPy)]n(Py = 吡啶基;X = OMe、H、Br 和 Cl)配合物,生成具有 Cu-SCN 网络的二维 (2D) 结构。本文还报告了[Cu(SCN)(3-OMePy)]n 的单晶结构。X = OMe 和 H 的配合物显示出类似的结构,其中的二维层类似于硅烯或蓝色磷烯的屈曲二维片。另一方面,对于 X = Br 和 Cl 的络合物,其波纹状二维结构类似于黑色磷烯中的皱褶二维薄片。研究发现,取代基团吸电子能力的变化会系统地改变配合物的电子能级和带隙,从而使基于 CuSCN 的二维材料在可见光范围内显示出光学吸收和发射。此外,第一原理计算显示,电子能级的急剧变化是由于在 SCN 状态之下出现了 Py 配体电子状态。这项研究表明,二维铜-氯化萘网络的结构、电子和光学特性可以通过配体修饰进行系统定制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Molecular Systems Design & Engineering
Molecular Systems Design & Engineering Engineering-Biomedical Engineering
CiteScore
6.40
自引率
2.80%
发文量
144
期刊介绍: Molecular Systems Design & Engineering provides a hub for cutting-edge research into how understanding of molecular properties, behaviour and interactions can be used to design and assemble better materials, systems, and processes to achieve specific functions. These may have applications of technological significance and help address global challenges.
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