TY - JOUR
T1 - Construction of C-C bonds via photoreductive coupling of ketones and aldehydes in the metal-organic framework MFM-300(Cr)
AU - Luo, Tian
AU - Li, Lili
AU - Chen, Yinlin
AU - An, Jie
AU - Liu, Chengcheng
AU - Yan, Zheng
AU - Carter, Joseph
AU - Han, Xue
AU - Sheveleva, Alena
AU - Tuna, Floriana
AU - Mcinnes, Eric
AU - Tang, Chiu
AU - Schroder, Martin
AU - Yang, Sihai
N1 - Funding Information:
We thank EPSRC (EP/I011870), University of Manchester and the National Natural Science Foundation of China (NSFC 21602248) for funding, and EPSRC for funding of the EPSRC National EPR Facility at Manchester. J.A. and S.Y. were supported by a Royal Society International Exchange Grant (IE161216). This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 742401, NANOCHEM). We are grateful to Diamond Light Source for access to Beamline I11. The XPS measurement were conducted in the Henry Royce Institute for Advanced Materials, funded through EPSRC grants EP/R00661X/1, EP/S019367/1, EP/P025021/1 and EP/P025498/1. We thank D. Leonori for helpful discussions. A.M.S. is supported by a Royal Society Newton International Fellowship. Z.Y. acknowledges the financial support from Chinese Scholarship Council.
Publisher Copyright:
© 2021, The Author(s).
PY - 2021/6/11
Y1 - 2021/6/11
N2 - Construction of C-C bonds via reductive coupling of aldehydes and ketones is hindered by the highly negative reduction potential of these carbonyl substrates, particularly ketones, and this renders the formation of ketyl radicals extremely endergonic. Here, we report the efficient activation of carbonyl compounds by the formation of specific host-guest interactions in a hydroxyl-decorated porous photocatalyst. MFM-300(Cr) exhibits a band gap of 1.75 eV and shows excellent catalytic activity and stability towards the photoreductive coupling of 30 different aldehydes and ketones to the corresponding 1,2-diols at room temperature. Synchrotron X-ray diffraction and electron paramagnetic resonance spectroscopy confirm the generation of ketyl radicals via confinement within MFM-300(Cr). This protocol removes simultaneously the need for a precious metal-based photocatalyst or for amine-based sacrificial agents for the photochemical synthesis.
AB - Construction of C-C bonds via reductive coupling of aldehydes and ketones is hindered by the highly negative reduction potential of these carbonyl substrates, particularly ketones, and this renders the formation of ketyl radicals extremely endergonic. Here, we report the efficient activation of carbonyl compounds by the formation of specific host-guest interactions in a hydroxyl-decorated porous photocatalyst. MFM-300(Cr) exhibits a band gap of 1.75 eV and shows excellent catalytic activity and stability towards the photoreductive coupling of 30 different aldehydes and ketones to the corresponding 1,2-diols at room temperature. Synchrotron X-ray diffraction and electron paramagnetic resonance spectroscopy confirm the generation of ketyl radicals via confinement within MFM-300(Cr). This protocol removes simultaneously the need for a precious metal-based photocatalyst or for amine-based sacrificial agents for the photochemical synthesis.
UR - http://www.scopus.com/inward/record.url?scp=85107647569&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/6d799acc-606f-3eb2-bc59-95c3115710d4/
U2 - 10.1038/s41467-021-23302-w
DO - 10.1038/s41467-021-23302-w
M3 - Article
C2 - 34117225
SN - 2041-1723
VL - 12
SP - 1
EP - 10
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 3583
ER -