Bandgap Engineering of Erbium‐Metallofullerenes toward Switchable Photoluminescence

Author:

Jin Huaimin1ORCID,Xin Jinpeng1,Xiang Wenhao1,Jiang Zhanxin1,Han Xinyi1,Chen Muqing1,Du Pingwu1,Yao Yang‐Rong1ORCID,Yang Shangfeng1ORCID

Affiliation:

1. Key Laboratory of Precision and Intelligent Chemistry Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) Department of Materials Science and Engineering University of Science and Technology of China Hefei 230026 China

Abstract

AbstractEncapsulating photoluminescent lanthanide ions like erbium (Er) into fullerene cages affords photoluminescent endohedral metallofullerenes (EMFs). Few reported photoluminescent Er‐EMFs are all based on encapsulation of multiple (two to three) metal atoms, whereas mono‐Er‐EMFs exemplified by Er@C82 are not photoluminescent due to its narrow optical bandgap. Herein, by entrapping an Er‐cyanide cluster into various C82 cages to form novel Er‐monometallic cyanide clusterfullerenes (CYCFs), ErCN@C82 (C2(5), Cs(6), and C2v(9)), the photoluminescent properties of CYCFs are investigated, and obvious near‐infrared (NIR) photoluminescence only is observed for ErCN@C2(5)‐C82. Combined with a comparative photoluminescence study of three medium‐bandgap di‐Er‐EMFs, including Er2@Cs(6)‐C82, Er2O@Cs(6)‐C82, and Er2C2@Cs(6)‐C82, this study proposes that the optical bandgap can be used as a simple criterion for switching the photoluminescence of Er‐EMFs, and the bandgap threshold is determined to be between 0.83 and 0.74 eV. Furthermore, the photoluminescent patterns of these three di‐Er‐EMFs differ dramatically. It is found that the location of the Er atom within the same Cs(6)‐C82 cage is almost fixed and independent on the endo‐unit; thus the previous statement on the key role of metal position in photoluminescence of di‐Er‐EMFs seems erroneous, and the geometric configuration of the endo‐unit, especially the bridging mode of two Er ions, is decisive instead.

Funder

National Natural Science Foundation of China

Fundamental Research Funds for the Central Universities

Natural Science Foundation of Anhui Province

Publisher

Wiley

Subject

Mechanical Engineering,Mechanics of Materials,General Materials Science

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