10.1002/chem.201803635
Chemistry - A European Journal
COMMUNICATION
9
Zr-RuBPY
6h
6h
81%
26%
>10:1
>10:1
Acknowledgements
Cl(4c)
Me (5a)
6e
UiO-
Ru(bpy)3
10
We thank the NSF (DMR-1308229) for funding support.
[a] Reaction conditions: 2.5 eq. Michael acceptor, 1 mol% Zr-RuBPYor UiO-
Ru(bpy)3, 2 eq. DIPEA, 4 eq. LiBF4, 6 mW/cm2 410 nm LED, MeCN (0.1M). [b]
Isolated yields. [c] Diastereomer ratios determined by NMR.
Keywords: metal-organic layer • metal-organic framework,
photocatalysis • photosensitizer • diffusion
[1]
[2]
G. Ciamician, Science 1912, 36, 385.
The superior photocatalytic activity of Zr-RuBPY over UiO-
Ru(bpy)3 was also demonstrated in Meerwein addition reactions
(Table 4).[36] Zr-RuBPY efficiently catalyzed three-component
Meerwein addition reactions between aryl diazonium salts,
styrenes, and nitriles under LED irradiation to afford desired
products in 55-83% yields. In contrast, UiO-Ru(bpy)3 produced
desired products in much lower 0-21% yields. The difference in
photocatalytic activities of Zr-RuBPY over UiO-Ru(bpy)3 is likely
due to the ease of intermediate and substrate diffusion in 2-D
MOLs but not 3-D MOFs.
J. M. R. Narayanam, C. R. J. Stephenson, Chem. Soc. Rev. 2011, 40,
102-113.
[3]
[4]
X. Deng, Z. Li, H. García, Chem. Eur. J. 2017, 23, 11189-11209.
M. H. Shaw, J. Twilton, D. W. C. MacMillan, J. Org. Chem. 2016, 81,
6898-6926.
[5]
[6]
[7]
[8]
[9]
M. A. Ischay, M. E. Anzovino, J. Du, T. P. Yoon, J. Am. Chem. Soc. 2008,
130, 12886-12887.
J. M. R. Narayanam, J. W. Tucker, C. R. J. Stephenson, J. Am. Chem.
Soc. 2009, 131, 8756-8757.
E. L. Tyson, M. S. Ament, T. P. Yoon, J. Org. Chem. 2013, 78, 2046-
2050.
S. Fukuzumi, T. Kishi, H. Kotani, Y.-M. Lee, W. Nam, Nat. Chem. 2010,
3, 38.
Table 4. Meerwein addition reactions.[a]
J. Twilton, C. Le, P. Zhang, M. H. Shaw, R. W. Evans, D. W. C. MacMillan,
Nat. Rev. Chem. 2017, 1, 0052.
[10] M. Jouffroy, D. N. Primer, G. A. Molander, J. Am. Chem. Soc. 2016, 138,
475-478.
[11] T. R. Blum, Z. D. Miller, D. M. Bates, I. A. Guzei, T. P. Yoon, Science
2016, 354, 1391.
[12] Z. D. Miller, B. J. Lee, T. P. Yoon, Angew. Chem., Int. Ed. 2017, 56,
11891-11895.
Diazonium
Salt (R1 = )
Styrene
(R2 = )
Entry
Nitrile
Adduct
Catalyst
Yield[b]
83%
<10%
55%
n.r.
[13] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science 2013,
341.
1
2
Zr-RuBPY
2-NO2 (7a)
4-OMe (7b)
H (7c)
H (8a)
H (8a)
H (8a)
MeCN
9a
UiO-
Ru(bpy)3
[14] Y. Cui, B. Li, H. He, W. Zhou, B. Chen, G. Qian, Acc. Chem. Res. 2016,
49, 483-493.
3
Zr-RuBPY
[15] J. Tian, P. K. Thallapally, B. P. McGrail, CrystEngComm. 2012, 14, 1909-
1919.
MeCN
MeCN
9b
9c
9d
9e
UiO-
Ru(bpy)3
4
[16] C. Wang, Z. Xie, K. E. deKrafft, W. Lin, J. Am. Chem. Soc. 2011, 133,
13445-13454.
5
Zr-RuBPY
76%
<5%
76%
21%
62%
15%
UiO-
Ru(bpy)3
[17] C. Wang, K. E. deKrafft, W. Lin, J. Am. Chem. Soc. 2012, 134, 7211-
7214.
6
7
Zr-RuBPY
[18] M.-H. Xie, X.-L. Yang, C. Zou, C.-D. Wu, Inorg. Chem. 2011, 50, 5318-
5320.
COOH
(8b)
2-NO2 (7a)
2-NO2 (7a)
MeCN
UiO-
Ru(bpy)3
8
[19] P. Wu, C. He, J. Wang, X. Peng, X. Li, Y. An, C. Duan, J. Am. Chem.
Soc. 2012, 134, 14991-14999.
9
Zr-RuBPY
[20] A. Fateeva, A. Chater Philip, P. Ireland Christopher, A. Tahir Asif, Z.
Khimyak Yaroslav, V. Wiper Paul, R. Darwent James, J. Rosseinsky
Matthew, Angew. Chem., Int. Ed. 2012, 51, 7440-7444.
[21] X. Yu, S. M. Cohen, Chem. Commun. 2015, 51, 9880-9883.
[22] X. Yu, S. M. Cohen, J. Am. Chem. Soc. 2016, 138, 12320-12323.
[23] J. A. Johnson, J. Luo, X. Zhang, Y.-S. Chen, M. D. Morton, E. Echeverría,
F. E. Torres, J. Zhang, ACS Catal. 2015, 5, 5283-5291.
[24] A. Dhakshinamoorthy, M. Alvaro, Y. K. Hwang, Y.-K. Seo, A. Corma, H.
Garcia, Dalton Trans. 2011, 40, 10719-10724.
H (8a)
ClCH2CN
UiO-
Ru(bpy)3
10
[a] Reaction conditions: 1 eq. diazonium salt, 2 eq. styrene, 0.5% Zr-RuBPY or
UiO-(bpy)3, 1 eq. H2O, 6 mW/cm2 410 nm LED, MeCN or ClCH2CN (0.25M),
room temperature. [b] Isolated yields.
In summary, we synthesized photoactive Zr-RuBPY MOL via
post-synthetic incorporation of Ru(bpy)32+ into the backbone of Zr-
BPY MOL. Zr-RuBPY was shown to be an efficient
heterogeneous photocatalyst for intra/intermolecular [2+2]
cycloaddition and Meerwein addition reactions under visible-light
irradiation. In contrast, the corresponding MOF catalyst failed in
these photoreactions, due to either pore size limitation or
restricted diffusion of reactive intermediates. Our work highlights
the potential of MOLs in catalyzing a variety of multicomponent
photoreactions.
[25] S. Horike, M. Dincǎ, K. Tamaki, J. R. Long, J. Am. Chem. Soc. 2008, 130,
5854-5855.
[26] C. Wang, W. Lin, J. Am. Chem. Soc. 2011, 133, 4232-4235.
[27] C. Wang, J.-L. Wang, W. Lin, J. Am. Chem. Soc. 2012, 134, 19895-
19908.
[28] L. Cao, Z. Lin, F. Peng, W. Wang, R. Huang, C. Wang, J. Yan, J. Liang,
Z. Zhang, T. Zhang, L. Long, J. Sun, W. Lin, Angew. Chem., Int. Ed. 2016,
55, 4962-4966.
[29] Z. Lin, N. C. Thacker, T. Sawano, T. Drake, P. Ji, G. Lan, L. Cao, S. Liu,
C. Wang, W. Lin, Chem. Sci. 2018, 9, 143-151.
[30] G. Lan, K. Ni, R. Xu, K. Lu, Z. Lin, C. Chan, W. Lin, Angew. Chem., Int.
Ed. 2017, 56, 12102-12106.
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