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Comparisons of bpy and phen Ligand Backbones in Cr-Mediated (Co-)Electrocatalytic CO 2 Reduction
- Award ID(s):
- 2018870
- NSF-PAR ID:
- 10459057
- Date Published:
- Journal Name:
- Organometallics
- Volume:
- 42
- Issue:
- 11
- ISSN:
- 0276-7333
- Page Range / eLocation ID:
- 1139 to 1148
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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null (Ed.)Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I , Rb 2 Mn 3 (VO 4 ) 2 CO 3 , crystallizes in the trigonal crystal system in the space group P 3̄1 c , and compound II , K 2 Co 3 (VO 4 ) 2 CO 3 , crystallizes in the hexagonal space group P 6 3 / m . Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO 6 octahedra and MO 5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c -axis through tetrahedral [VO 4 ] groups. The MO 5 units are connected with each other by carbonate groups in the ab -plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO 6 -honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO 5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K 2 Co 3 (VO 4 ) 2 CO 3 ( II ) exhibits a canted antiferromagnetic ordering below T N = 8 K. The Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of −42 K suggesting a dominant antiferromagnetic coupling in the Co 2+ magnetic sublattices.more » « less