10.1002/anie.202007520
Angewandte Chemie International Edition
RESEARCH ARTICLE
O. Voznyy, S. Kinge, Z. Lu, S. O. Kelley, A. Amassian, J. Tang, E.
H. Sargent, Nat. Photonics 2020, 14, 227-233; b) Y. Yuan, H. Zhu,
X. Wang, D. Cui, Z. Gao, D. Su, J. Zhao, O. Chen, Chem. Mater.
2019, 31, 2635-2643; c) O. Chen, H. Wei, A. Maurice, M. Bawendi,
P. Reiss, MRS Bull. 2013, 38, 696-702; d) M. V. Kovalenko, L.
Manna, A. Cabot, Z. Hens, D. V. Talapin, C. R. Kagan, V. I. Klimov,
A. L. Rogach, P. Reiss, D. J. Milliron, P. Guyot-Sionnnest, G.
Konstantatos, W. J. Parak, T. Hyeon, B. A. Korgel, C. B. Murray, W.
Heiss, ACS Nano 2015, 9, 1012-1057; e) T. Cai, W. Shi, S. Hwang,
K. Kobbekaduwa, Y. Nagaoka, H. Yang, K. Hills-Kimball, H. Zhu, J.
Wang, Z. Wang, Y. Liu, D. Su, J. Gao, O. Chen, J. Am. Chem.Soc.
2020, 142, 11927-11936.
a) K. Chen, X. Deng, G. Dodekatos, H. Tüysüz, J. Am. Chem. Soc.
2017, 139, 12267-12273; b) Q. Guo, F. Liang, X.-B. Li, Y.-J. Gao,
M.-Y. Huang, Y. Wang, S.-G. Xia, X.-Y. Gao, Q.-C. Gan, Z.-S. Lin,
C.-H. Tung, L.-Z. Wu, Chem 2019, 5, 2605-2616; c) K. P.
McClelland, E. A. Weiss, ACS Appl. Energy Mater. 2019, 2, 92-96.
a) W. Wu, G. Liu, Q. Xie, S. Liang, H. Zheng, R. Yuan, W. Su, L.
Wu, Green Chem. 2012, 14, 1705-1709; b) S. C. Jensen, S. Bettis
Homan, E. A. Weiss, J. Am. Chem.Soc. 2016, 138, 1591-1600; c)
X. Zhu, Y. Lin, Y. Sun, M. C. Beard, Y. Yan, J. Am. Chem.Soc. 2019,
141, 733-738.
Information). The result of undetectable dimer products further
supports the proposed monomer radical mediated reaction
mechanism (Figure 5).
Conclusion
In conclusion, we show the first example of stereoselective C–C
oxidative dimerization reaction photocatalyzed by ZW-capped
CsPbBr3 perovskite QD under visible light illumination. High
stereoselectivities (>99%) of dl-isomer are demonstrated by
dimerizing two α-aryl ketonitriles. We found that the ZW ligand
coverage is crucial to stabilize/recycle the QD catalysts as well as
enhance their photocatalytic reactivity. Moreover, we expand the
reaction scope by investigating a series of starting substrate
materials with different substituents on the aryl ring and varied
functional moieties. We show that EDGs on the para-position of
the aryl ring or an extended conjugated π system is necessity for
efficient dimerization reactions to occur. Furthermore,
mechanistic studies reveal a free-radical mediated reaction
pathway with the steric hinderance effect being largely
responsible for the observed stereoselectivity. Our study shows
that lead-halide perovskite QDs with an optimized ligand
[6]
[7]
[8]
a) J. A. Caputo, L. C. Frenette, N. Zhao, K. L. Sowers, T. D. Krauss,
D. J. Weix, J. Am. Chem. Soc. 2017, 139, 4250-4253; b) Z. Zhang,
K. Edme, S. Lian, E. A. Weiss, J. Am. Chem. Soc. 2017, 139, 4246-
4249; c) Z. Hong, W. K. Chong, A. Y. R. Ng, M. Li, R. Ganguly, T.
C. Sum, H. S. Soo, Angew. Chem. Int. Ed. 2019, 58, 3456-3460; d)
Y. Jiang, C. Wang, C. Rogers, M. S. Kodaimati, E. Weiss, C. Nat.
Chem. , 2019, 11, 1034-1040; e) X. Zhu, Y. Lin, J. San Martin, Y.
Sun, D. Zhu, Y. Yan, Nat. Commun. 2019, 10, 2843.
[9]
W. W. Yu, L. Qu, W. Guo, X. Peng, Chem. Mater. 2003, 15, 2854-
2860.
[10]
a) O. Chen, J. Zhao, V. P. Chauhan, J. Cui, C. Wong, D. K. Harris,
H. Wei, H.-S. Han, D. Fukumura, R. K. Jain, M. G. Bawendi, Nat.
Mater. 2013, 12, 445-451; b) Q. Zhong, M. Cao, Y. Xu, P. Li, Y.
Zhang, H. Hu, D. Yang, Y. Xu, L. Wang, Y. Li, X. Zhang, Q. Zhang,
Nano Lett. 2019, 19, 4151-4157.
passivation hold
photocatalysts in
a
a
great potential of acting as efficient
range of organic transformations with
improved product yield and high selectivity.
[11]
a) R. Tan, Y. Yuan, Y. Nagaoka, D. Eggert, X. Wang, S. Thota, P.
Guo, H. Yang, J. Zhao, O. Chen, Chem. Mater. 2017, 29, 4097-
4108; b) L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R.
Caputo, C. H. Hendon, R. X. Yang, A. Walsh, M. V. Kovalenko,
Nano Lett. 2015, 15, 3692-3696.
Acknowledgements
[12]
[13]
M. S. Kodaimati, K. P. McClelland, C. He, S. Lian, Y. Jiang, Z. Zhang,
E. A. Weiss, Inorg. Chem. 2018, 57, 3659-3670.
a) C. Huang, X.-B. Li, C.-H. Tung, L.-Z. Wu, Chem. Eur. J. 2018, 24,
11530-11534; b) I. N. Chakraborty, S. Roy, G. Devatha, A. Rao, P.
P. Pillai, Chem. Mater. 2019, 31, 2258-2262.
O.C. acknowledges the supports from Brown University startup
funds and the National Science Foundation (CBET-1936223 and
DMR-1943930). TEM measurements were performed at the
Electron Microscopy Facility in IMNI at Brown University.
[14]
[15]
A. Pal, I. Ghosh, S. Sapra, B. König, Chem. Mater. 2017, 29, 5225-
5231.
a) H. Huang, H. Yuan, K. P. F. Janssen, G. Solís-Fernández, Y.
Wang, C. Y. X. Tan, D. Jonckheere, E. Debroye, J. Long, J. Hendrix,
J. Hofkens, J. A. Steele, M. B. J. Roeffaers, ACS Energy Lett. 2018,
3, 755-759; b) S. Schünemann, M. van Gastel, H. Tüysüz,
ChemSusChem 2018, 11, 2057-2061; c) S. Xie, Z. Shen, J. Deng,
P. Guo, Q. Zhang, H. Zhang, C. Ma, Z. Jiang, J. Cheng, D. Deng, Y.
Wang, Nat. Commun. 2018, 9, 1181.
Y. Huang, Y. Zhu, E. Egap, ACS Macro Lett. 2018, 7, 184-189.
a) J. Hu, T.-J. Pu, Z.-W. Xu, W.-Y. Xu, Y.-S. Feng, Adv. Synth. Catal.
2019, 361, 708-713; b) Y. Jiang, C. Wang, C. R. Rogers, M. S.
Kodaimati, E. A. Weiss, Nat. Chem. 2019, 11, 1034-1040.
J. De Roo, M. Ibáñez, P. Geiregat, G. Nedelcu, W. Walravens, J.
Maes, J. C. Martins, I. Van Driessche, M. V. Kovalenko, Z. Hens,
ACS Nano 2016, 10, 2071-2081.
Z. Zhang, Y. Liang, H. Huang, X. Liu, Q. Li, L. Chen, D. Xu, Angew.
Chem. Int. Ed. 2019, 58, 7263-7267.
W.-B. Wu, Y.-C. Wong, Z.-K. Tan, J. Wu, Catal. Sci. Technol. 2018,
8, 4257-4263.
a) H. A. P. De Jongh, C. R. H. I. De Jonge, W. J. Mijs, J. Org. Chem.
1971, 36, 3160-3168; b) Y. Du, Y. Zhang, S. Wang, K. Zhao, Synlett
2009, 2009, 1835-1841.
L. Liu, Y. Fan, Q. He, Y. Zhang, D. Zhang-Negrerie, J. Huang, Y.
Du, K. Zhao, J. Org. Chem. 2012, 77, 3997-4004.
F. Krieg, S. T. Ochsenbein, S. Yakunin, S. ten Brinck, P. Aellen, A.
Süess, B. Clerc, D. Guggisberg, O. Nazarenko, Y. Shynkarenko, S.
Kumar, C.-J. Shih, I. Infante, M. V. Kovalenko, ACS Energy Lett.
2018, 3, 641-646.
Z. Liang, W. Hou, Y. Du, Y. Zhang, Y. Pan, D. Mao, K. Zhao, Org.
Lett. 2009, 11, 4978-4981.
a) Z. Pan, H. Zhang, K. Cheng, Y. Hou, J. Hua, X. Zhong, ACS Nano
2012, 6, 3982-3991; b) P. Wang, M. Wang, J. Zhang, C. Li, X. Xu,
Y. Jin, ACS Appl. Mater. Interfaces 2017, 9, 35712-35720.
D. Griller, K. U. Ingold, Acc. Chem. Res. 1976, 9, 13-19.
K. Hills-Kimball, M. J. Pérez, Y. Nagaoka, T. Cai, H. Yang, A. H.
Davis, W. Zheng, O. Chen, Chem. Mater. 2020, 32, 2489-2500.
Keywords: photocatalysis • C-C coupling • dimerization •
CsPbBr3 perovskite QDs • stereoselectivity
[1]
a) G. H. Carey, A. L. Abdelhady, Z. Ning, S. M. Thon, O. M. Bakr, E.
H. Sargent, Chem. Rev. 2015, 115, 12732-12763; b) H. Yang, Y.
Zhang, K. Hills-Kimball, Y. Zhou, O. Chen, Sustain. Energy & Fuels
2018, 2, 2381-2397; c) J. Wang, Y. Yuan, H. Zhu, T. Cai, Y. Fang,
O. Chen, Nano Energy 2020, 67, 104217.
[16]
[17]
[2]
a) I. L. Medintz, H. T. Uyeda, E. R. Goldman, H. Mattoussi, Nat.
Mater. 2005, 4, 435-446; b) J. K. Jaiswal, S. M. Simon, Trends Cell
Biol. 2004, 14, 497-504; c) M.-K. So, C. Xu, A. M. Loening, S. S.
Gambhir, J. Rao, Nat. Biotechnol. 2006, 24, 339-343; d) M. Heine,
A. W. Fischer, C. Schlein, C. Jung, L. G. Straub, K. Gottschling, N.
Mangels, Y. Yuan, S. K. Nilsson, G. Liebscher, O. Chen, R.
Schreiber, R. Zechner, L. Scheja, J. Heeren, Cell Metab. 2018, 28,
644-655; e) O. T. Bruns, T. S. Bischof, D. K. Harris, D. Franke, Y.
Shi, L. Riedemann, A. Bartelt, F. B. Jaworski, J. A. Carr, C. J.
Rowlands, M. W. B. Wilson, O. Chen, H. Wei, G. W. Hwang, D. M.
Montana, I. Coropceanu, O. B. Achorn, J. Kloepper, J. Heeren, P.
T. C. So, D. Fukumura, K. F. Jensen, R. K. Jain, M. G. Bawendi,
Nat. Biomed. Eng. 2017, 1, 0056.
[18]
[19]
[20]
[21]
[22]
[23]
[3]
a) Q. Sun, Y. A. Wang, L. S. Li, D. Wang, T. Zhu, J. Xu, C. Yang, Y.
Li, Nat. Photonics 2007, 1, 717-722; b) X. Dai, Z. Zhang, Y. Jin, Y.
Niu, H. Cao, X. Liang, L. Chen, J. Wang, X. Peng, Nature 2014, 515,
96-99; c) L. Qian, Y. Zheng, J. Xue, P. H. Holloway, Nat. Photonics
2011, 5, 543-548; d) Y.-H. Won, O. Cho, T. Kim, D.-Y. Chung, T.
Kim, H. Chung, H. Jang, J. Lee, D. Kim, E. Jang, Nature 2019, 575,
634-638.
[24]
[25]
[4]
[5]
a) M. Lu, Y. Zhang, S. X. Wang, J. Guo, W. W. Yu, A. L. Rogach,
Adv. Funct. Mater. 2019, 29, 1902008; b) E. Jang, Y. Kim, Y. H.
Won, H. Jang, S. M. Choi, ACS Energy Lett. 2020, 5, 1316-1327; c)
J. H. Jo, D. Y. Jo, S. H. Lee, S. Y. Yoon, H. B. Lim, B. J. Lee, Y. R.
Do, H. Yang, ACS Appl. Nano Mater. 2020, 3, 1972-1980.
a) L. Gao, L. N. Quan, F. P. García de Arquer, Y. Zhao, R. Munir, A.
Proppe, R. Quintero-Bermudez, C. Zou, Z. Yang, M. I. Saidaminov,
[26]
[27]
[28]
L. I. Peterson, J. Am. Chem. Soc. 1967, 89, 2677-2681.
6
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