硫化铜簇的配体修饰以增强三阶非线性光学响应,Crystal Growth & Design

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硫化铜簇的配体修饰以增强三阶非线性光学响应
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2023-07-20 , DOI: 10.1021/acs.cgd.3c00675
Yu-Jia Cheng _{1,

2,

3} , Ran-Ran Wu _{1,

2,

3} , Jian-Qiang Zhao ₂ , Er-Xia Chen _{2,

4} , Xuechou Zhou ₅ , Yumei Dai ₆ , Hui-Li Zheng ₂ , Qipu Lin _{2,

3,

4}

Affiliation

两个硫化铜(I)簇被烷基硫醇和共轭N,S-杂环配体协同修饰，即Cu ₆ ( ^t BuS) ₂ (MBIZ) ₄ (命名为Cu ₆ )和Cu ₈ ( ^t BuS) ₄ ( MBIZ) ₄ ·CH ₃ OH·2H ₂ O（指定为Cu ₈）（MBIZ = 2-巯基苯并咪唑；^t BuS =叔-丁基硫醇）。引入更多的硫醇配体导致簇核进一步生长，导致从八面体构型转变为双四面体构型，同时Cu…Cu距离略有增加。值得注意的是，由于表面配体的修饰，这两个簇都表现出高化学稳定性和超疏水性，在较宽的 pH 范围（Cu 6 为 1-14，Cu 8 为3-11 _）中_稳定至少1 周。此外，Cu ₈表现出近红外（NIR）光致发光（PL）发射和更好的三阶非线性光学（NLO）性能，非线性吸收系数（β）为3.5 × 10 –10 m/W，是普通材料的3.5^倍。铜₆且优于大多数晶体硫族化物半导体。理论计算表明，有机配体和簇核以调节光学性质的方式共同优化电子构型。这项工作为在原子精确水平上理解簇核/表面组成与光学性质之间的关系提供了新的视角，这有助于准确设计和合成稳定高效的三阶非线性光学材料。

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Ligand Modification on Copper(I)-Sulfide Clusters for Enhanced Third-Order Nonlinear Optical Response

Two copper(I)-sulfide clusters were synergistically modified by alkylthiols and conjugated N,S-heterocyclic ligands, i.e., Cu₆(^tBuS)₂(MBIZ)₄ (designated as Cu₆) and Cu₈(^tBuS)₄(MBIZ)₄·CH₃OH·2H₂O (designated as Cu₈) (MBIZ = 2-mercaptobenzimidazole; ^tBuS = tert-butyl mercaptan). Introducing more thiol ligands led to further growth of the cluster core, resulting in the transformation from an octahedral to a di-tetrahedral configuration, accompanied by a slight increase in the Cu···Cu distance. Notably, both clusters demonstrate high chemical stability and superhydrophobicity as a result of the modification with surface ligands, being stable at least 1 week in a wide range of pH (1–14 for Cu₆ and 3–11 for Cu₈). Moreover, Cu₈ exhibited near-infrared (NIR) photoluminescence (PL) emission and better third-order nonlinear optical (NLO) performance, with nonlinear absorption coefficients (β) of 3.5 × 10^–10 m/W, 3.5 times than that of Cu₆ and superior to the majority of crystalline chalcogenide semiconductors. Theoretical calculations indicate that the organic ligands and cluster core jointly optimize the electronic configuration in a manner that regulates the optical properties. This work provides a new perspective into understanding the relationship between cluster core/surface compositions and optical properties at an atomically precise level, which is instrumental in the accurate design and synthesis of stable and efficient third-order NLO materials.

更新日期：2023-07-20

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