Enantiopure Chiral Au13 Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO2
Source abstract
Abstract
A series of chiral Au 13 nanoclusters were synthesized via the direct reduction of chiral dinuclear Au(I) halide complexes ligated by chiral dioxalone-linked bis- N -heterocyclic carbene (bisNHC) ligands. Electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations confirmed the molecular formula to be [Au 13 (bisNHC) 4 I 4 ] +, with a chiral arrangement of the four ditopic NHC ligands around the icosahedral Au 13 core. Circular dichroism (CD) spectroscopy of the two enantiomers of the Au 13 clusters shows distinct mirror images of the enantiomers and supports chirality transfer from ligands to the metal core. A plausible model structure was built with the assistance of theoretical analysis, and DFT calculations were employed to explain the origin of the optical and CD activities and their dependence on the binding arrangement of the ditopic bisNHC ligands. The clusters show remarkable stability with minimal decomposition in various solutions both at elevated and room temperatures. The potential of these clusters as nanocatalysts in the electrocatalytic reduction of CO 2 to CO is described.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Nanocluster Synthesis and Applications · Metal-Organic Frameworks: Synthesis and Applications · Catalytic C–H Functionalization Methods
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Chemistry, Queen’s University, Chernoff Hall, Kingston, Ontario K7L 3N6, Canada
Carbon to Metal Coating Institute-C2MCI, Queen’s University, Kingston, Ontario K7L 3N6, Canada
Departments of Chemistry and Physics, Nanoscience Center, University of Jyväskylä, Jyväskylä 40014, Finland
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Department of Earth and Environmental Sciences, Graduate School of Environmental Studies, Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan
Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, Nagoya 464-8602, Japan
Funding
Social Sciences and Humanities Research Council of Canada · Ministry of Education, Culture, Sports, Science and Technology · Canada Foundation for Innovation · Japan Society for the Promotion of Science · Research Foundation for the Electrotechnology of Chubu · American Chemical Society Petroleum Research Fund · Natural Sciences and Engineering Research Council of Canada
References (87)
Show source-provided references
1. 10.1039/b517312b10.1039/b517312b ↗
2. 10.1021/acs.chemrev.6b0076910.1021/acs.chemrev.6b00769 ↗
3. 10.1039/C4NR05794E10.1039/C4NR05794E ↗
4. 10.1039/C9CS00633H10.1039/C9CS00633H ↗
5. Pradeep T. · 2023 · 1
6. 10.1021/acs.accounts.8b0038010.1021/acs.accounts.8b00380 ↗
7. 10.1021/acs.chemrev.5b0070310.1021/acs.chemrev.5b00703 ↗
8. 10.1126/sciadv.170116210.1126/sciadv.1701162 ↗
9. 10.1021/cr068366310.1021/cr0683663 ↗
10. 10.1039/c0dt00399a10.1039/c0dt00399a ↗
11. 10.1039/b410399h10.1039/b410399h ↗
12. 10.1038/ncomms187710.1038/ncomms1877 ↗
13. 10.1021/acs.nanolett.0c0165910.1021/acs.nanolett.0c01659 ↗
14. 10.1002/cnma.20220019410.1002/cnma.202200194 ↗
15. 10.1080/23746149.2018.150972710.1080/23746149.2018.1509727 ↗
16. 10.1021/accountsmr.0c0005710.1021/accountsmr.0c00057 ↗
17. 10.1002/adom.20190215210.1002/adom.201902152 ↗
18. 10.1002/asia.20170002310.1002/asia.201700023 ↗
19. 10.1021/ar400295d10.1021/ar400295d ↗
20. 10.1021/acs.jpcc.5b1023510.1021/acs.jpcc.5b10235 ↗
21. 10.1021/acs.chemrev.6b0075510.1021/acs.chemrev.6b00755 ↗
22. 10.1021/acs.accounts.8b0037610.1021/acs.accounts.8b00376 ↗
23. 10.1007/s12274-017-1935-210.1007/s12274-017-1935-2 ↗
24. 10.1038/s41467-018-03136-910.1038/s41467-018-03136-9 ↗
25. 10.1002/anie.20060476010.1002/anie.200604760 ↗
26. 10.1021/jp503395910.1021/jp5033959 ↗
27. 10.1002/anie.20130859910.1002/anie.201308599 ↗
28. 10.1021/jp993691y10.1021/jp993691y ↗
29. 10.1021/jp061670f10.1021/jp061670f ↗
30. 10.1021/ja053504b10.1021/ja053504b ↗
31. 10.1021/acs.jpclett.6b0229410.1021/acs.jpclett.6b02294 ↗
32. 10.1021/acs.inorgchem.8b0317110.1021/acs.inorgchem.8b03171 ↗
33. 10.1126/science.114862410.1126/science.1148624 ↗
34. 10.1021/ja500809p10.1021/ja500809p ↗
35. 10.1021/ja102934q10.1021/ja102934q ↗
36. 10.1002/smll.20090239810.1002/smll.200902398 ↗
37. 10.1038/ncomms180210.1038/ncomms1802 ↗
38. 10.1002/anie.20120236910.1002/anie.201202369 ↗
39. 10.1021/ja404058q10.1021/ja404058q ↗
40. 10.1038/ncomms811710.1038/ncomms8117 ↗
41. 10.1007/s12274-017-1935-210.1007/s12274-017-1935-2 ↗
42. 10.1002/anie.20140466510.1002/anie.201404665 ↗
43. 10.1021/jacs.7b0902510.1021/jacs.7b09025 ↗
44. 10.1002/adom.20200193610.1002/adom.202001936 ↗
45. 10.1246/bcsj.2021006010.1246/bcsj.20210060 ↗
46. 10.1021/acs.jpcc.2c0637010.1021/acs.jpcc.2c06370 ↗
47. 10.1021/jacs.2c0078910.1021/jacs.2c00789 ↗
48. 10.1021/acsnanoscienceau.2c0002610.1021/acsnanoscienceau.2c00026 ↗
49. 10.1021/acs.inorgchem.2c0025610.1021/acs.inorgchem.2c00256 ↗
50. 10.1021/jacsau.2c0000410.1021/jacsau.2c00004 ↗
51. 10.1021/jacs.1c1045010.1021/jacs.1c10450 ↗
52. 10.1021/jacs.1c1185710.1021/jacs.1c11857 ↗
53. 10.1038/s41557-019-0246-510.1038/s41557-019-0246-5 ↗
54. 10.1021/acs.organomet.8b0029110.1021/acs.organomet.8b00291 ↗
55. 10.1002/anie.20120671210.1002/anie.201206712 ↗
56. 10.1002/anie.20190898310.1002/anie.201908983 ↗
57. 10.1021/jacs.9b0785410.1021/jacs.9b07854 ↗
58. 10.1007/s12274-020-2685-010.1007/s12274-020-2685-0 ↗
59. 10.1039/D0CC01482F10.1039/D0CC01482F ↗
60. 10.1039/D1SC03076K10.1039/D1SC03076K ↗
61. 10.1002/anie.20201371810.1002/anie.202013718 ↗
62. 10.1021/acs.jpcc.1c0219710.1021/acs.jpcc.1c02197 ↗
63. 10.1002/anie.20221901710.1002/anie.202219017 ↗
64. 10.1002/anie.20160430110.1002/anie.201604301 ↗
65. 10.1021/jo00128a02910.1021/jo00128a029 ↗
66. 10.1039/b922534j10.1039/b922534j ↗
67. 10.1039/c3cc43076f10.1039/c3cc43076f ↗
68. 10.1039/df950090001410.1039/df9500900014 ↗
69. 10.1039/C8RA08751B10.1039/C8RA08751B ↗
70. 10.1021/jo00412a02210.1021/jo00412a022 ↗
71. 10.1021/acsnano.3c0656810.1021/acsnano.3c06568 ↗
72. 10.1021/acs.jpclett.3c0296510.1021/acs.jpclett.3c02965 ↗
73. 10.1021/acs.inorgchem.2c0333110.1021/acs.inorgchem.2c03331 ↗
74. 10.1002/anie.20210329010.1002/anie.202103290 ↗
75. 10.1021/ja507568910.1021/ja5075689 ↗
76. 10.1088/0953-8984/22/25/25320210.1088/0953-8984/22/25/253202 ↗
77. 10.1103/PhysRevLett.77.386510.1103/PhysRevLett.77.3865 ↗
78. 10.1007/BF0116130110.1007/BF01161301 ↗
79. 10.1103/physrevb.82.11510610.1103/physrevb.82.115106 ↗
80. 10.1063/1.294313810.1063/1.2943138 ↗
81. 10.1021/acs.chemmater.1c0093610.1021/acs.chemmater.1c00936 ↗
82. 10.1021/jacs.9b0822810.1021/jacs.9b08228 ↗
83. 10.1021/jacs.9b0805510.1021/jacs.9b08055 ↗
84. 10.1038/ncomms1472310.1038/ncomms14723 ↗
85. 10.1021/acssuschemeng.8b0419010.1021/acssuschemeng.8b04190 ↗
86. 10.1039/D0RA00738B10.1039/D0RA00738B ↗
87. 10.1039/C8DT00109J10.1039/C8DT00109J ↗