In Situ Metal–Ligand Reactions under Solvent-Dependent Hydro(solvo)thermal Conditions: Structures, Mass Spectrometry, and Magnetism

Abstract

In this study, four in situ hydro­(solvo)­thermal metal–ligand reactions, including oxidation (H2L1), C–C coupling (H4L2), nitration (H2L3), and condensation (HL4–6), based on bis­[3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]­methane (H2L0), in the presence of DyIII ions, were carried out. The in situ metal–ligand reaction gave six new ligands existing in eight novel DyIII coordination complexes, which were characterized by crystal structure, mass spectrometry, and magnetism.

Syntheses, Structures, and Properties of Coordination Polymers with 2,5-Dihydroxy-1,4-Benzoquinone and 4,4′-Bipyridyl Synthesized by In Situ Hydrolysis Method

“…Density functional theory (DFT) calculations were performed using Gaussian16 software . All geometry optimizations were performed at the UB3LYP/6-31G+(d,p) level of theory. − Elemental analyses were performed using the J-Science Lab JM-10 equipped in the Research and Analytical Center for Giant Molecules at Tohoku University. Single crystal X-ray crystal structure analyses were performed using a Rigaku Varimax diffractometer with a Mo Kα radiation source.…”

Manipulating Solvothermal Coordination-Catalyzed In Situ Tandem Reactions to Construct Dysprosium-Based Complexes with Different Shapes and Zero-Field SMM Behaviors

“…28−32 The selection of suitable organic ligands with active functional groups is the premise of coordination-driven in situ tandem reactions. 9,13,24 The study of lanthanide complexes has been favored by chemists due to their applications in luminescence, magnetism, catalysis, and separation. 33−37 Dy(III) ions possess Ising-type magnetic anisotropy originating from the Kramer double ground state and are preferred components for building single-molecule magnets (SMMs), which have important significance and potential applications in the fields of density data storage, molecular spintronics, and quantum computing.…”

“…Precisely controlled synthesis has been achieved from small molecules to macromolecules, from single molecular primitive to supramolecular systems. − With the continuous development of synthesis and characterization techniques, chemists have increasingly focused on synthetic chemistry and developed many synthesis methods that reached an unprecedented level of maturity at the technical level. − In addition, as human society pays an increasing amount of attention to issues such as environmental energy, synthetic chemistry that people pursue is economical and energy-saving chemistry. Therefore, the atom economy and utilization in the synthesis reaction need to be the focus of research, and the reaction process needs to be faster, simpler, and more efficient. − In recent years, in situ tandem reactions became some of the preferred synthetic strategies that mainly utilize in situ coordination catalysis. − When metal ions are involved in the in situ tandem reaction, in the traditional metal ion in situ coordination catalysis process, the metal ion first undergoes coordination and then activation. Finally, the metal ion leaves.…”

“…So far, solvothermal black-box reactions are among the most widely used methods for the synthesis of lanthanide multinuclear clusters; however, in this process, organic ligands participate only in coordination to form complexes. − The selection of suitable organic ligands with active functional groups is the premise of coordination-driven in situ tandem reactions. ,, The study of lanthanide complexes has been favored by chemists due to their applications in luminescence, magnetism, catalysis, and separation. − Dy­(III) ions possess Ising-type magnetic anisotropy originating from the Kramer double ground state and are preferred components for building single-molecule magnets (SMMs), which have important significance and potential applications in the fields of density data storage, molecular spintronics, and quantum computing. − After years of exploration, many mononuclear Dy-based SMMs with excellent blocking temperatures and energy barriers have emerged. − For example, in 2018, Tong’s group realized the key parameters for regulating the mononuclear dysprosium complexes through the design of ligands and obtained the axial crystal field, and finally achieved the first breakthrough with a T B temperature of 80 K and U eff as high as 2217 K . In 2016, Zheng’s group reported that a Dy-based SMM was obtained by adjusting the coordination environment, with a U eff = 1815 K and a T B of 14 K .…”

The Stepwise Formation of {Gd4} Clusters with Magnetocaloric Effect, Accompanied by In Situ Condensation Cyclization Reactions

“…Inspired by a Dy 4 cluster reported by our group previously, which had been constructed from in situ metal–ligand reactions from bis­[3-(pyridin-2-yl)-1H-1,2,4-triazole-5-yl]­methane (bptm), three Gd 4 clusters [Gd 4 (L 1 ) 2 (μ 3 -OH) 2 (NO 3 ) 2 (Ac) 6 ] ( 1 ), [Gd 4 (L 2 ) 2 (μ 3 -OH) 2 (NO 3 ) 2 (Ac) 6 ] ( 2 ), and [Gd 4 (L 3 ) 2 (μ 3 -OH) 2 (NO 3 ) 2 (Ac) 6 ] ( 3 ) were successfully synthesized by the ligand (bptm, 5-bptm, and 4-bptm) with metal Gd salts (Gd­(NO 3 ) 3 ·6H 2 O:Gd­(Ac) 3 ·4H 2 O = 1:1) under hydro­(solvo)­thermal conditions. The Gd 4 clusters of 1 – 3 exhibited an inverted symmetrical structure, and the four Gd 3+ ions were precisely coplanar.…”