Ultrabright Au@Cu14 nanoclusters: 71.3% phosphorescence quantum yield in non-degassed solution at room temperature

被引:122
作者
Song, Yongbo [1 ]
Li, Yingwei [2 ]
Zhou, Meng [3 ]
Liu, Xuan [4 ,5 ]
Li, Hao [4 ,5 ]
Wang, He [3 ]
Shen, Yuhua [4 ,5 ]
Zhu, Manzhou [4 ,5 ]
Jin, Rongchao [2 ]
机构
[1] Anhui Med Univ, Sch Biomed Engn, Hefei 230032, Anhui, Peoples R China
[2] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
[3] Univ Miami, Dept Phys, Coral Gables, FL 33146 USA
[4] Anhui Univ, Dept Chem, Hefei 230601, Anhui, Peoples R China
[5] Anhui Univ, Ctr Atom Engn Adv Mat, Anhui Prov Key Lab Chem Inorgan Organ Hybrid Func, Hefei 230601, Anhui, Peoples R China
关键词
CRYSTAL-STRUCTURE; COPPER(I); LUMINESCENCE; CLUSTERS; PHOTOLUMINESCENCE; FLUORESCENCE; AGGREGATION; COMPLEXES; EMISSION; LIGANDS;
D O I
10.1126/sciadv.abd2091
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
The photoluminescence of metal nanoclusters is typically low, and phosphorescence emission is rare due to ultra-fast free-electron dynamics and quenching by phonons. Here, we report an electronic engineering approach to achieving very high phosphorescence (quantum yield 71.3%) from a [Au@Cu-14((SPhBu)-Bu-t)(12)(PPh(C2H4CN)(2))(6)](+) nanocluster (abbreviated Au@Cu-14) in non-degassed solution at room temperature. The structure of Au@Cu-14 has a single-Au-atom kernel, which is encapsulated by a rigid Cu(I) complex cage. This core-shell structure leads to highly efficient singlet-to-triplet intersystem crossing and suppression of nonradiative energy loss. Unlike the phosphorescent organic materials and organometallic complexes-which require de-aerated conditions due to severe quenching by air (i.e., O-2)-the phosphorescence from Au@Cu-14 is much less sensitive to air, which is important for lighting and biomedical applications.
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页数:6
相关论文
共 52 条
[1]   Photochemistry and photophysics of coordination compounds: Copper [J].
Armaroli, Nicola ;
Accorsi, Gianluca ;
Cardinali, Francois ;
Listorti, Andrea .
PHOTOCHEMISTRY AND PHOTOPHYSICS OF COORDINATION COMPOUNDS I, 2007, 280 :69-115
[2]   Theory and Calculation of the Phosphorescence Phenomenon [J].
Baryshnikov, Gleb ;
Minaev, Boris ;
Agren, Hans .
CHEMICAL REVIEWS, 2017, 117 (09) :6500-6537
[3]   Direct observation of intersystem crossing in a thermally activated delayed fluorescence copper complex in the solid state [J].
Bergmann, Larissa ;
Hedley, Gordon J. ;
Baumann, Thomas ;
Braese, Stefan ;
Samuel, Ifor D. W. .
SCIENCE ADVANCES, 2016, 2 (01)
[4]  
Bourhis LJ, 2015, ACTA CRYSTALLOGR A, V71, P59, DOI [10.1107/S2053273314022207, 10.1107/S205327331402220759]
[5]   Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster [J].
Chakrahari, Kiran Kumarvarma ;
Silalahi, Rhone P. Brocha ;
Liao, Jian-Hong ;
Kahlal, Samia ;
Liu, Yu-Chiao ;
Lee, Jyh-Fu ;
Chiang, Ming-Hsi ;
Saillard, Jean-Yves ;
Liu, C. W. .
CHEMICAL SCIENCE, 2018, 9 (33) :6785-6795
[6]   [Cu13{S2CNnBu2}6(acetylide)4]+: A Two-Electron Superatom [J].
Chakrahari, Kiran Kumarvarma ;
Liao, Jian-Hong ;
Kahlal, Samia ;
Liu, Yu-Chiao ;
Chiang, Ming-Hsi ;
Saillard, Jean-Yves ;
Liu, C. W. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (47) :14704-14708
[7]   OLEX2: a complete structure solution, refinement and analysis program [J].
Dolomanov, Oleg V. ;
Bourhis, Luc J. ;
Gildea, Richard J. ;
Howard, Judith A. K. ;
Puschmann, Horst .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2009, 42 :339-341
[8]  
Du BJ, 2017, NAT NANOTECHNOL, V12, P1096, DOI [10.1038/NNANO.2017.170, 10.1038/nnano.2017.170]
[9]   Photoluminescence properties of multinuclear copper(I) compounds [J].
Ford, PC ;
Cariati, E ;
Bourassa, J .
CHEMICAL REVIEWS, 1999, 99 (12) :3625-3647
[10]   Origin of the bright photoluminescence of few-atom silver clusters confined in LTA zeolites [J].
Grandjean, Didier ;
Coutino-Gonzalez, Eduardo ;
Ngo Tuan Cuong ;
Fron, Eduard ;
Baekelant, Wouter ;
Aghakhani, Saleh ;
Schlexer, Philomena ;
D'Acapito, Francesco ;
Banerjee, Dipanjan ;
Roeffaers, Maarten B. J. ;
Minh Tho Nguyen ;
Hofkens, Johan ;
Lievens, Peter .
SCIENCE, 2018, 361 (6403) :686-689