A 3D MOF based on Adamantoid Tetracopper(II) and Aminophosphine Oxide Cages: Structural Features and Magnetic and Catalytic Properties

Abstract

This work describes an unexpected generation of a new 3D metal–organic framework (MOF), [Cu 4 (μ-Cl) 6 (μ 4 -O)Cu(OH) 2 (μ-PTA=O) 4 ] n ·2 n Cl-EtOH·2.5 n H 2 O, from copper(II) chloride and 1,3,5-triaza-7-phosphaadamantane 7-oxide (PTA=O). The obtained product is composed of diamandoid tetracopper(II) [Cu 4 (μ-Cl) 6 (μ 4 -O)] cages and monocopper(II) [Cu(OH) 2 ] units that are assembled, via the diamandoid μ-PTA=O linkers, into an intricate 3D net with an nbo topology. Magnetic susceptibility measurements on this MOF in the temperature range of 1.8–300 K reveal a ferromagnetic interaction ( J = +20 cm –1 ) between the neighboring copper(II) ions. Single-point DFT calculations disclose a strong delocalization of the spin density over the tetranuclear unit. The magnitude of exchange coupling, predicted from the broken-symmetry DFT studies, is in good agreement with the experimental data. This copper(II) compound also acts as an active catalyst for the mild oxidation and carboxylation of alkanes. The present study provides a unique example of an MOF that is assembled from two different types of adamantoid Cu 4 and PTA=O cages, thus contributing to widening a diversity of functional metal–organic frameworks.

[Ag4Br6] cluster-based 3D bromoargentate hybrid: crystal structure, optical/photoelectrical performance and theoretical study

“…Unlike other templates, the Hmta ligand and its derivative may provide an effective approach to direct the novel haloargentate/halocuprate hybrid characteristic of diverse SBUs. In addition to the [Ag 18,19,21,22,33 which are unique and rarely found in most Ag/Cu-based metal halides (Fig. 2).…”

“…Unlike other templates, the Hmta ligand and its derivative may provide an effective approach to direct the novel haloargentate/halocuprate hybrid characteristic of diverse SBUs. In addition to the [Ag4 Br 6 ] cluster, the documented examples of this also include [Ag 4 I 4 ], [Ag 5 I 6 ], [Ag 8 I 6 ], [Cu 4 I 6 ], [Cu 6 Cl 6 ], [Cu 5 Cl 6 ], and [Cu 4 Cl 6 O],18,19,21,22,33 which are unique and rarely found in most Ag/Cu-based metal halides (Fig.2).…”

Structural Diversity and Catalytic Properties of Coordination Polymers with Functionalized Naphthalene Dicarboxylate Linkers

“…The research field of coordination polymers (CPs) has witnessed a remarkable expansion since its discovery in the mid-20th century. This is due to their unique and versatile properties, which can be tailored by manipulating their structures’ organic ligand and metallic ion components. − The structural diversity results in a lot of applications, such as sensing, − gas sorption, − heterogeneous catalysis, − etc., making CPs a subject of continued interest in the field of materials chemistry.…”

“…In catalysis, the significance of CPs lies in their high selectivity, activity, and facile recovery, particularly for heterogeneous catalysis due to their limited solubility in a range of organic solvents. Therefore, the application of coordination polymers in the field of catalysis has been paid more and more attention by scientists. − The Henry reaction, called nitroaldol transformation, is a crucial method for forming bonds between carbon–carbon atoms in organic chemistry. This process involves mixing nitroalkanes with carbonyl substances like aldehydes and ketones to produce β-nitro alcohol products.…”

Future Paradigm of 3D Printed Ni-Based Metal Organic Framework Catalysts for Dry Methane Reforming: Techno-economic and Environmental Analyses

“…Over the last decade, the synthesis of nano-engineered metal–organic frameworks (MOFs) has shown a tremendous development with reassuring application in catalysis processes, aligning with the Principles of Green Chemistry of ″Design of Energy Efficiency″, ″Use of Renewable Feedstocks″, and ″Catalysis″. , Due to the unique features such as intrinsic porosity, large surface area, tunable characteristic, long life span, and low density, MOFs are expected to offer desired improvements in contemporary organic chemistry and modern organometallic catalysis. , One of the most promising approaches for the application of MOF-based heterogeneous catalysts is thermal carbonization, including pyrolysis, DRM, and Fischer–Tropsch synthesis . MOFs have been introduced into the carbonization field, where these hybrid materials are used as sacrificial templates.…”