Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation

ABSTRACT The restriction of the molecular motion has been extensively exploited in tailoring the photoluminescence (PL) of metal nanoclusters, while the activation of such a restriction at the molecular level remains highly challenging. In this work, a two‐step strategy, that is, surface activating...

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Main Authors: Jian Zhu, Rui Zhao, Honglei Shen, Chen Zhu, Meng Zhou, Xi Kang, Manzhou Zhu
Format: Article
Language:English
Published: Wiley 2025-03-01
Series:Aggregate
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Online Access:https://doi.org/10.1002/agt2.720
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author Jian Zhu
Rui Zhao
Honglei Shen
Chen Zhu
Meng Zhou
Xi Kang
Manzhou Zhu
author_facet Jian Zhu
Rui Zhao
Honglei Shen
Chen Zhu
Meng Zhou
Xi Kang
Manzhou Zhu
author_sort Jian Zhu
collection DOAJ
description ABSTRACT The restriction of the molecular motion has been extensively exploited in tailoring the photoluminescence (PL) of metal nanoclusters, while the activation of such a restriction at the molecular level remains highly challenging. In this work, a two‐step strategy, that is, surface activating and surface coupling, was proposed to induce the restriction of the molecular motion of nanoclusters at the molecular level, and the corresponding nanoclusters underwent emission appearance and enhancement. The peripheral phosphine ligand functionalization and alkali metal cation introduction gave rise to a series of structural‐correlated M+‐incorporated Cu14 nanoclusters (M = Li, Na, K, Rb, Cs) with a surface‐aggregation characteristic, among which the K+‐participating nanocluster displayed the strongest fluorescence intensity in both solution and crystal states. Atomic‐level structure–property correlations were investigated to rationalize the PL comparisons. Overall, this work offers a new perspective for regulating the PL of metal nanoclusters via restricting their molecular motions, hopefully providing insight into the fabrication of highly emissive metal nanoclusters and cluster‐based nanomaterials.
format Article
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issn 2692-4560
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spelling doaj-art-e5f3e01ebc81426cb4c34ac3decfa8312025-08-20T01:48:25ZengWileyAggregate2692-45602025-03-0163n/an/a10.1002/agt2.720Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence ManipulationJian Zhu0Rui Zhao1Honglei Shen2Chen Zhu3Meng Zhou4Xi Kang5Manzhou Zhu6Department of Chemistry and Centre for Atomic Engineering of Advanced Materials Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei Anhui People's Republic of ChinaHefei National Research Center for Physical Sciences at the Microscale, Department of Chemical Physics University of Science and Technology of China Hefei Anhui People's Republic of ChinaDepartment of Chemistry and Centre for Atomic Engineering of Advanced Materials Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei Anhui People's Republic of ChinaDepartment of Chemistry and Centre for Atomic Engineering of Advanced Materials Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei Anhui People's Republic of ChinaHefei National Research Center for Physical Sciences at the Microscale, Department of Chemical Physics University of Science and Technology of China Hefei Anhui People's Republic of ChinaDepartment of Chemistry and Centre for Atomic Engineering of Advanced Materials Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei Anhui People's Republic of ChinaDepartment of Chemistry and Centre for Atomic Engineering of Advanced Materials Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials Anhui University Hefei Anhui People's Republic of ChinaABSTRACT The restriction of the molecular motion has been extensively exploited in tailoring the photoluminescence (PL) of metal nanoclusters, while the activation of such a restriction at the molecular level remains highly challenging. In this work, a two‐step strategy, that is, surface activating and surface coupling, was proposed to induce the restriction of the molecular motion of nanoclusters at the molecular level, and the corresponding nanoclusters underwent emission appearance and enhancement. The peripheral phosphine ligand functionalization and alkali metal cation introduction gave rise to a series of structural‐correlated M+‐incorporated Cu14 nanoclusters (M = Li, Na, K, Rb, Cs) with a surface‐aggregation characteristic, among which the K+‐participating nanocluster displayed the strongest fluorescence intensity in both solution and crystal states. Atomic‐level structure–property correlations were investigated to rationalize the PL comparisons. Overall, this work offers a new perspective for regulating the PL of metal nanoclusters via restricting their molecular motions, hopefully providing insight into the fabrication of highly emissive metal nanoclusters and cluster‐based nanomaterials.https://doi.org/10.1002/agt2.720aggregation‐induced emissionatomically precise nanoclustersphotoluminescencesurface activatingsurface coupling
spellingShingle Jian Zhu
Rui Zhao
Honglei Shen
Chen Zhu
Meng Zhou
Xi Kang
Manzhou Zhu
Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation
Aggregate
aggregation‐induced emission
atomically precise nanoclusters
photoluminescence
surface activating
surface coupling
title Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation
title_full Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation
title_fullStr Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation
title_full_unstemmed Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation
title_short Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation
title_sort intramolecular aggregation induced surface coupling of metal nanoclusters structure elucidation and photoluminescence manipulation
topic aggregation‐induced emission
atomically precise nanoclusters
photoluminescence
surface activating
surface coupling
url https://doi.org/10.1002/agt2.720
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AT ruizhao intramolecularaggregationinducedsurfacecouplingofmetalnanoclustersstructureelucidationandphotoluminescencemanipulation
AT hongleishen intramolecularaggregationinducedsurfacecouplingofmetalnanoclustersstructureelucidationandphotoluminescencemanipulation
AT chenzhu intramolecularaggregationinducedsurfacecouplingofmetalnanoclustersstructureelucidationandphotoluminescencemanipulation
AT mengzhou intramolecularaggregationinducedsurfacecouplingofmetalnanoclustersstructureelucidationandphotoluminescencemanipulation
AT xikang intramolecularaggregationinducedsurfacecouplingofmetalnanoclustersstructureelucidationandphotoluminescencemanipulation
AT manzhouzhu intramolecularaggregationinducedsurfacecouplingofmetalnanoclustersstructureelucidationandphotoluminescencemanipulation