Synthesis, Structural, and Physicochemical Characterization of a Ti₆ and a Unique Type of Zr₆ Oxo Clusters Bearing an Electron-Rich Unsymmetrical {OON} Catecholate/Oxime Ligand and Exhibiting Metalloaromaticity

Abstract

Synthesis, structural, and physicochemical characterization of a Ti6 and a unique type of Zr6 oxo clusters bearing an electron-rich unsymmetrical {OON} catecholate/oxime ligand and exhibiting metalloaromaticity. Inorganic Chemistry, 59(24), pp. 18345-18357.

The forgotten chemistry of group(IV) metals: A survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters

“…Mixing ZrCl4 and 2,3-dihydroxybenzaldehyde oxime (H3dihybo) in the presence of Bu4NOH in methanol afforded the cluster 12). [93] This structure features a trigonal-prismatic arrangement of the six Zr atoms, in which all the Zr atoms are seven coordinated with a pentagonal-bipyramid geometry, and can be seen as an stacked variant of the Zr3 clusters reported previously (Figure 7). In fact, both the hexanuclear metal core and its Zr3 A similar stacked architecture was observed also when using tridentate phosphonate ligands…”

“…•CH3OH is more similar to the decked Ti18 cluster discussed below, due to the oxygen bridge between layers than to the staggered Ti6 structure highlighted here (Figure 30). [93] Notably, a similar stacked Ti6 cluster has been reported, which interestingly, also contains tridentate ligands like H2dihybo. [129]…”

Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

“…Chemical exchange between the two coordinated Hdihybe − ligands is supported by the much broader 1 H peaks of 1 than the respective peaks of H 2 dihybe. The carbonylic 13 C NMR peak of the CD 3 OD solution of 1, determined by 2D grHSQC and gr HMBC spectroscopies (Figures S3-S6), shows the largest shift compared to the respective peak of the ligand, ∆δ = −3.9 ppm, suggesting coordination of Ti IV to the carbonylic oxygen atom [24,[58][59][60][61].…”

“…Moreover, the 3.20 eV band-gap of TiO 2 limits its applications in photocatalysis [ 22 , 23 ]. However, the use of strong organic chelators allows the modulation of the band-gap with subsequent Vis-NIR absorption by PTCs to appropriate values, which is a fundamentally important parameter for practical applications [ 24 ].…”

Acid/base responsive assembly/dis-assembly of a family of zirconium(iv) clusters with a cyclic imide-dioxime ligand

“…MOCs of group IV are a very promising class of compounds with many applications. [1][2][3][4][5][6][7][8][9] In particular, the study of zirconium oxo clusters (ZrOCs) is of vital importance since they are processable molecular analogues of ZrO 2 which has a wide range of applications in fuel cells, 10 photocatalysis, 11,12 and photochemical water splitting. 13 Moreover, various ZrOCs have been reported as molecule-based building blocks in the construction of metal-organic frameworks (MOFs), with numerous applications in gas storage and separation, [14][15][16][17] adsorption, [18][19][20][21] catalysis, [22][23][24][25] and drug delivery.…”