All‐ <i>Nido</i> ‐Carborane‐Protected Copper Clusters

X Xuan‐Hui Zhao (Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry Zhengzhou University Zhengzhou 450001 China) J Jie Wang (State Key Laboratory of Molecular Oncology, Beijing Key Laboratory, CAMS Key Laboratory of Translational Research on Lung Cancer, Department of Medical Oncology Cancer Hospital, Chinese Academy of Medical Sciences Beijing China) Y Yubing Si (College of Chemistry) J Jia‐Hua Hu (Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry Zhengzhou University Zhengzhou 450001 China) X Xi‐Ming Luo (Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry Zhengzhou University Zhengzhou 450001 China) Z Zhao‐Yang Wang (Henan Key Laboratory of Crystalline Molecular Functional Materials Key Laboratory of Special Functional Molecular Materials (Zhengzhou University) Ministry of Education College of Chemistry Zhengzhou University Zhengzhou P. R. China) S Shuang‐Quan Zang (Henan Key Laboratory of Crystalline Molecular Functional Materials Key Laboratory of Special Functional Molecular Materials (Zhengzhou University) Ministry of Education Pingyuan Laboratory Zhengzhou University Zhengzhou China)

Abstract

Abstract Peripheral ligands of metal nanoclusters play a crucial role in determining their structures and modulating their physicochemical properties. Therefore, expanding the diversity of ligands is of paramount importance for advancing metal cluster science. In this work, we report for the first time the synthesis and characterization of two all‐ nido ‐carborane‐protected copper nanoclusters: an octahedral [Cu 6 (C 2 B 9 H 11 ) 4 ](Et 4 N) 2 ( Cu 6 ) and an icosahedral [Cu 13 (C 2 B 9 H 11 ) 6 ](Et 4 N) 3 ( Cu 13 ) (Et 4 N = tetraethylammonium). As confirmed by ESI‐MS and time‐dependent UV–vis absorption spectroscopy, Cu 6 undergoes spontaneous transformation into Cu 13 in acetone solution. Theoretical computations reveal that the superatomic cluster Cu 13 possesses an open‐shell electronic structure of 1S 2 1P 2 . Moreover, Cu 13 solution exhibits prominent near‐infrared luminescence at 880 nm and demonstrates superior performance in bioimaging with 4T1 cells, showcasing significant potential for biomedical applications. This study not only enriches the ligand library for metal clusters but also provides new impetus for the exploration of carborane chemistry.

Article Details

Volume / Issue Vol. 64, Issue 52
Published December 22, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (7)

X

Xuan‐Hui Zhao

Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry Zhengzhou University Zhengzhou 450001 China

J

Jie Wang

State Key Laboratory of Molecular Oncology, Beijing Key Laboratory, CAMS Key Laboratory of Translational Research on Lung Cancer, Department of Medical Oncology Cancer Hospital, Chinese Academy of Medical Sciences Beijing China

Y

Yubing Si

College of Chemistry

J

Jia‐Hua Hu

Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry Zhengzhou University Zhengzhou 450001 China

X

Xi‐Ming Luo

Henan Key Laboratory of Crystalline Molecular Functional Materials College of Chemistry Zhengzhou University Zhengzhou 450001 China

Z

Zhao‐Yang Wang

Henan Key Laboratory of Crystalline Molecular Functional Materials Key Laboratory of Special Functional Molecular Materials (Zhengzhou University) Ministry of Education College of Chemistry Zhengzhou University Zhengzhou P. R. China

S

Shuang‐Quan Zang

Henan Key Laboratory of Crystalline Molecular Functional Materials Key Laboratory of Special Functional Molecular Materials (Zhengzhou University) Ministry of Education Pingyuan Laboratory Zhengzhou University Zhengzhou China