一种具有大二次谐波产生响应的基于纳米团簇的叔丁基乙炔银（I）化合物的合成与表征

Synthesis and characterization of a nanocluster-based silver(i) tert-butylethynide compound with a large second-harmonic generation response.

作者信息

Hu Ting, Hu Chunli, Li Yuhang, Meng Lingyi, Xie Yiming, Liao Mingyue, Zhong Guiming, Lu Can-Zhong

机构信息

CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian Province, P. R. China.

College of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, P. R. China.

出版信息

Nanoscale. 2020 Jun 11;12(22):11847-11857. doi: 10.1039/d0nr03364b.

DOI:10.1039/d0nr03364b

PMID:32469355

Abstract

A new nanocluster-based silver(i) tert-butylethynide compound, namely, (tBuC[triple bond, length as m-dash]CAg)2(Ag4SiW12O40)(DMSO)6 (HT-1), has been synthesized and structurally characterized by X-ray crystallography. The two kinds of nanocluster synthons (a silver aggregate named [(tBuC[triple bond, length as m-dash]C)2Ag6(DMSO)6] and a SiW12 polyoxoanion) are assembled into a three-dimensional coordination network, which has a non-centrosymmetric crystal lattice. Powder second-harmonic generation (SHG) measurements reveal that HT-1 belongs to the phase-matchable class with a moderately strong SHG response of about 3 times that of the KH2PO4 (KDP) sample. HT-1 represents the first example of a Ag(i) alkynyl cluster compound with a SHG response. The present study not only extends the application fields of Ag(i) alkynyl clusters but also demonstrates a new paradigm for understanding the Ag(i) alkynyl structural chemistry.

摘要

一种基于纳米团簇的新型叔丁基乙炔银（I）化合物，即(tBuC≡CAg)2(Ag4SiW12O40)(DMSO)6（HT-1），已通过X射线晶体学进行了合成和结构表征。两种纳米团簇合成子（一种名为[(tBuC≡C)2Ag6(DMSO)6]的银聚集体和一种SiW12多金属氧酸盐阴离子）组装成一个三维配位网络，该网络具有非中心对称的晶格。粉末二次谐波产生（SHG）测量表明，HT-1属于相位匹配类，具有中等强度的SHG响应，约为KH2PO4（KDP）样品的3倍。HT-1是具有SHG响应的Ag（I）炔基簇化合物的首个实例。本研究不仅扩展了Ag（I）炔基簇的应用领域，还展示了理解Ag（I）炔基结构化学的新范例。