长期探寻的Au_(23)(S-Adm)_(16)结构及未曾预期的掺杂效应  

Long-Pursued Structure of Au_(23)(S-Adm)_(16) and the Unexpected Doping Effects

作　　者：冯磊 朱泽敏 杨颖 何宗兵 邹家丰 李漫波 赵燕 伍志鲲 Lei Feng;Ze-Min Zhu;Ying Yang;Zongbin He;Jiafeng Zou;Man-Bo Li;Yan Zhao;Zhikun Wu(Institute of Physical Science and Information Technology,Anhui University,Hefei 230601,China;Key Laboratory of Materials Physics,Anhui Key Laboratory of Nanomaterials and Nanotechnology,CAS Center for Excellence in Nanoscience,Institute of Solid State Physics,Hefei Institutes of Physical Science,Chinese Academy of Sciences,Hefei 230031,China)

机构地区：[1]安徽大学物质科学与信息技术研究院,合肥230601 [2]中国科学院合肥物质科学研究院固体物理研究所,中国科学院材料物理重点实验室,安徽省纳米材料与技术重点实验室,中国科学院纳米卓越中心,合肥230031

出　　处：《物理化学学报》2024年第5期1-2,共2页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(21925303,21771186,21829501,21222301,21528303,21171170,92061110);中国科学院合肥研究院院长基金(BJPY2019A02);中国科学院合肥研究院十三五重点计划(KP-2017-16);中国科学院合肥科学中心协同创新项目(2020HSC-CIP005,2022HSC-CIP018);安徽省自然科学基金(2108085Y05);合肥微尺度物理科学国家实验室(KF2020102);安徽大学启动经费(S020318006/037)资助。

摘　　要：一锅同时获得单个金属原子掺杂的纳米团簇与母体团簇富有挑战性。这样的合成可排除微量杂质的影响,使得掺杂和未掺杂纳米团簇的性质对比更加合理可靠。在此,我们首次实现了这种合成,得到了长期追寻的纳米团簇Au_(23)(SAdm)_(16)和其单镉掺杂的Au_(22)Cd_1(S-Adm)_(16)纳米团簇,并通过单晶X射线晶体学解析了其结构。令人惊讶的是,与以前的报道结果相反,Au_(23)(S-Adm)_(16)比Au_(22)Cd_1(S-Adm)_(16)更稳定。另一方面,由于掺入镉原子后,内核Au―Au键长度增加,光激发电子转移阻力增加,导致Au_(22)Cd_1(S-Adm)_(16)吸收和发射强度明显下降。因而,不仅团簇的稳定性,而且团簇的吸收和发射强度也与内核Au―Au键的长度关联。这项工作表明了两种团簇结构上的微小差异就可导致光学、热稳定性等方面的显著区别,也为研究金属纳米团簇的构效关系提供了良好的借鉴。Metal nanoclusters are rising stars in material science,and one advantage is their atomically precise tunability.It is well known that metal doping can efficiently modify the properties of metal nanoclusters.In particular,without altering the parent nanocluster framework,doping a single heterometal atom can tailor the properties of metal nanoclusters and aid investigations of the structure–property relationship of metal nanoclusters.To our knowledge,the simultaneous synthesis of a single heterometaldoped nanocluster and its parent nanocluster is challenging and has not been previously reported;however,this is highly desirable because it can prevent the influence of trace impurities and allow comparison between doped and undoped nanoclusters.The single Cd-doped gold nanocluster Au_(22)Cd_1(S-Adm)_(16)(S-Adm=1-adamantanethiolate)has been previously synthesized and structurally elucidated.However,the structure of the parent nanocluster,Au_(23)(S-Adm)_(16),remains unknown,inspiring this investigation.In this study,we synthesized Au_(23)(S-Adm)_(16)and its single-doped Au_(22)Cd_1(S-Adm)_(16)nanocluster in one pot for the first time,and we resolved their structures using single-crystal X-ray crystallography.The structure of Au_(22)Cd_1(S-Adm)_(16)is similar to that of Au_(23)(S-Adm)_(16)except that a kernel Au atom in Au_(23)(S-Adm)_(16)is replaced with a Cd atom.This Cd replacement causes the kernel Au―Au bond length to increase owing to the loosening of the original closely packed structure.In contrast to prior reports,Au_(23)(S-Adm)_(16)is surprisingly more stable than Au_(22)Cd_1(S-Adm)_(16),as determined via ultraviolet visible-near infrared(UV-Vis-NIR)spectroscopy at 80℃.This stability was attributed to the decrease in the kernel Au―Au bond length.Although the maximum absorption of Au_(22)Cd_1(S-Adm)_(16)slightly red-shifted from 605 to 608 nm after Cd doping,the molar extinction coefficient of Au_(23)(S-Adm)_(16)at 605 nm was approximately twice that of Au_(22)Cd_1(S-Adm)_(16)at 608 nm.Thus,the increase

关 键 词：金属纳米团簇 合成 Au―Au键长 性质 构效关系 

分 类 号：O641[理学—物理化学]