首页|长期探寻的Au23(S-Adm)16结构及未曾预期的掺杂效应

长期探寻的Au23(S-Adm)16结构及未曾预期的掺杂效应

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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Au23(S-Adm)16和其单镉掺杂的Au22Cd1(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,Au23(S-Adm)16比Au22Cd1(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Au22Cd1(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.
Long-Pursued Structure of Au23(S-Adm)16 and the Unexpected Doping Effects
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 heterometal-doped 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 Au22Cd1(S-Adm)16(S-Adm=1-adamantanethiolate)has been previously synthesized and structurally elucidated.However,the structure of the parent nanocluster,Au23(S-Adm)16,remains unknown,inspiring this investigation.In this study,we synthesized Au23(S-Adm)16 and its single-doped Au22Cd1(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 Au22Cd1(S-Adm)16 is similar to that of Au23(S-Adm)16 except that a kernel Au atom in Au23(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,Au23(S-Adm)16 is surprisingly more stable than Au22Cd1(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 Au22Cd1(S-Adm)16 slightly red-shifted from 605 to 608 nm after Cd doping,the molar extinction coefficient of Au23(S-Adm)16 at 605 nm was approximately twice that of Au22Cd1(S-Adm)16 at 608 nm.Thus,the increase in kernel Au—Au bond length may decrease the photoexcitation electron transfer efficiency owing to lengthening of the photoexcitation electron transfer pathway.As further support for this opinion,although the two nanoclusters showed similar emission profiles and maxima(750 nm for Au23(S-Adm)16 and 760 nm for Au22Cd1(S-Adm)16),they exhibited obvious emission intensity differences.Specifically,the quantum yield of Au23(S-Adm)16(approximately 3.160×10-5)was found to be 1.13 times that of Au22Cd1(S-Adm)16(approximately 2.793×10-5).Thus,the stability and absorption and emission intensities correlate with the kernel Au—Au bond length.This study shows that two metal nanoclusters with slight structural differences can exhibit different properties in terms of optical and thermal stability,providing a good reference for studying their structure-property relationships.

Metal nanoclustersSynthesisAu—Au bond lengthPropertyProperty-structure correlation

冯磊、朱泽敏、杨颖、何宗兵、邹家丰、李漫波、赵燕、伍志鲲

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安徽大学物质科学与信息技术研究院,合肥 230601

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

金属纳米团簇 合成 Au—Au键长 性质 构效关系

国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金中国科学院合肥研究院院长基金中国科学院合肥研究院重点计划(十三五)中国科学院合肥科学中心协同创新项目中国科学院合肥科学中心协同创新项目安徽省自然科学基金合肥微尺度物理科学国家实验室项目安徽大学启动经费项目

21925303217711862182950121222301215283032117117092061110BJPY2019A02KP-2017-162020HSC-CIP0052022HSC-CIP0182108085Y05KF2020102S020318006/037

2024

10.3866/PKU.WHXB202305029

物理化学学报
中国化学会

物理化学学报

CSTPCD北大核心
影响因子：0.951
ISSN：1000-6818
年,卷(期)：2024.40(5)