Crystallographic and Spectroscopic Investigations on Oxidative Coordination in the Heteroleptic Mononuclear Complex of Cerium and Benzoxazine Dimer

Abstract

Among lanthanide-based compounds, cerium compounds exhibit a significant role in a variety of research fields due to their distinct tetravalency, high economic feasibility, and high stability of Ce(IV) complexes. Herein, a systematic investigation of crystallographic information, chemical properties, and mechanistic formation of the novel Ce(IV) complex synthesized from cerium(III) nitrate hexahydrate and 2,2′-(methylazanediyl)bis(methylene)bis(4-methylphenol) (MMD) ligand has been explored. According to the analysis of the crystallographic information, the obtained complex crystal consists of the Ce(IV) center coordinated with two nitrate ligands and two bidentate coordinated (N-protonated and O,O-deprotonated) MMD ligands. The fingerprint plots and the Hirshfeld surface analyses suggest that the C–H⋯O and C–H⋯π interactions significantly contribute to the crystal packing. The C–H⋯O and C–H⋯π contacts link the molecules into infinite molecular chains propagating along the [100] and [010] directions. Synchrotron powder X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques have been employed to gain an understanding of the oxidative complexation of Ce(IV)-MMD complex in detail. This finding would provide the possibility to systematically control the synthetic parameters and wisely design the precursor components in order to achieve the desired properties of novel materials for specific applications.

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

“…For example, Ce III -chloride, nitrate, triflate, and sulfate salts as well as Ce IV (SO 4 ) 2 all generated the Ce-10 cluster. Thus, Ce-10 formed irrespective of the Ce oxidation state in the starting materials, with oxidation of Ce III possibly occurring by action of ambient O 2 , 96 and reduction of Ce IV plausibly occurring via oxidation of acac 1– , as reported previously. 97 , 98 In addition to Ce-10 , two other structures built from Ce-10 were isolated (see Supporting Information ).…”

Tuning Compressive Young’s Moduli and Antibacterial Activities of Alginate/Poly(N-isopropylacrylamide) Hydrogels with Laponite Layers and Cerium Ions

“…The Ce–O stretching peak at around 600 cm –1 and N–O peaks at 1330 and 1040 cm –1 reveal the presence of Ce ions and nitrate groups, respectively, and together with the peaks of LP RD indicated above support the presence of the inorganic crosslinkers in the structures of single and double networks of PNIPAAm-based hybrid hydrogels. 42 …”

6,6′-((Methylazanedyl)bis(methylene))bis(2,4-dimethylphenol) Induces Autophagic Associated Cell Death through mTOR-Mediated Autophagy in Lung Cancer

“…Three N,N -bis(2-hydroxybenzyl) alkylamines, namely 2,2′-(methylazanediyl)bis(methylene)bis(4-ethylphenol) (EMD), 6,6′-(methylazanediyl)bis(methylene)bis(2,4-dimethylphenol) or (24MD), and 6,6′-(cyclohexylazanediyl)bis(methylene)bis(2,4-dimethylphenol) or (24CD), were synthesized according to the reactions illustrated in Figure 5 [ 21 , 50 , 51 , 52 , 53 ]. The first step was a one-pot Mannich reaction to form benzoxazine heterocycles, and the second step was a ring-opening reaction of the benzoxazines and phenols.…”