Deeply Reduced Chiral MoIV6-Polyoxometalates with Highly Enhanced Electronic Conductivity

• Published in: Inorganic chemistry Vol. 63; no. 35; p. 16374
• Main Authors: Li, Yankai, Sang, Ruili, Xu, Li
• Format: Journal Article
• Language: English
• Published: 02.09.2024
• DOI: 10.1021/acs.inorgchem.4c02338
• ISSN: 1520-510X

A series of deeply reduced MoIV6-polyoxometalates (POMs), [MoIV6(bpy)6MoVI2O16S2]·10H2O (1) (bpy = 2,2'-bipyridine), [MoIV6(bpy)4(L-TrA)2MoV4(bpy)2O14S4]2·36.5H2O (2), and [MoIV6(bpy)4(D-TrA)2MoV4(bpy)2O14S4]2 (3) (TrA = tartaric acid), were obtained from one-pot hydrothermal syntheses. They feature the bioxo-bridged [MoIV3O3S]4+ incomplete cuboidal cores stabilized by strong triangular metal-metal bonds and datively chelated bpy π-ligands. The two apical MoVIO4 in 12e-Mo8 (1) and two [MoV2O3STrAbpy] in 16e-Mo10 (2, 3) complete the octahedral coordination geometry of the deeply reduced MoIV, not counting the MoIV-MoIV d2-d2 bonds. The aromatic planar bpy π ligands form a two-dimensional face-to-face π stacking supramolecular structure, which are further strengthened by point-to-face C-H···π interactions in the π stacked layers. 16e-Mo10 (2, 3) has stronger intramolecular face-to-face π stacking interactions, which are interconnected by intermolecular C-H···π into a three-dimensional framework structure. These structural features account for their highly enhanced electronic conductivities (1, 6.19 × 10-8 S cm-1; 2, 2.18 × 10-7 S cm-1), providing a new way of thinking to improve electronic conductivity of POMs. 1-3 have been described by first-principles density function theory (DFT) calculations and also characterized by elemental analyses, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), solid UV-visible spectra, and circular dichroic (CD) spectra.A series of deeply reduced MoIV6-polyoxometalates (POMs), [MoIV6(bpy)6MoVI2O16S2]·10H2O (1) (bpy = 2,2'-bipyridine), [MoIV6(bpy)4(L-TrA)2MoV4(bpy)2O14S4]2·36.5H2O (2), and [MoIV6(bpy)4(D-TrA)2MoV4(bpy)2O14S4]2 (3) (TrA = tartaric acid), were obtained from one-pot hydrothermal syntheses. They feature the bioxo-bridged [MoIV3O3S]4+ incomplete cuboidal cores stabilized by strong triangular metal-metal bonds and datively chelated bpy π-ligands. The two apical MoVIO4 in 12e-Mo8 (1) and two [MoV2O3STrAbpy] in 16e-Mo10 (2, 3) complete the octahedral coordination geometry of the deeply reduced MoIV, not counting the MoIV-MoIV d2-d2 bonds. The aromatic planar bpy π ligands form a two-dimensional face-to-face π stacking supramolecular structure, which are further strengthened by point-to-face C-H···π interactions in the π stacked layers. 16e-Mo10 (2, 3) has stronger intramolecular face-to-face π stacking interactions, which are interconnected by intermolecular C-H···π into a three-dimensional framework structure. These structural features account for their highly enhanced electronic conductivities (1, 6.19 × 10-8 S cm-1; 2, 2.18 × 10-7 S cm-1), providing a new way of thinking to improve electronic conductivity of POMs. 1-3 have been described by first-principles density function theory (DFT) calculations and also characterized by elemental analyses, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), solid UV-visible spectra, and circular dichroic (CD) spectra.