Ligand-Directed Assembly of a Series of Complexes Bearing Thiourea-Based Carboxylates

Enhancement of Aqua‐Ammonia Vapor on Proton Conduction for Two Water‐Tolerant Complicated Copper Cluster Compounds

“…Since 1 has already been reported, we just briefly depict its crystal structure here. The single crystal X‐ray diffraction manifests that polymer 1 is a two‐dimensional reticular structure (Figure a), which pertains to monoclinic crystal system and P 2 1 / c space group . Note that the polymer contains carbonyl, thiocarbonyl, carboxylato and two –NH– groups and coordination water molecules, which will facilitate the formation of intramolecular and intermolecular hydrogen bonds in the framework.…”

“…Additionally, the new coordination sites can be added after the introduction of different amino acids into the acyl thiourea molecules, which lend more possibilities for the construction of complicated structural complexes. Consequently, our laboratory has already synthesized several complicated complexes bearing the acyl thiourea‐based carboxylate ligands, such as, two cluster polymers {[Cu I 6 Cu II 6 (BTEA) 6 (H 2 O) 3 (CH 3 OH) 6 ]⋅5H 2 O⋅3CH 3 OH} n (H 3 BTEA=2‐(3‐benzoylthioureido)ethanoic acid) and [Cu I 6 Cu II 6 (BTPA) 6 (H 2 O) 10 ] n (H 3 BTPA=2‐(3‐benzoylthioureido)propionic acid), and four dinuclear complexes [Ln 2 ( μ 2 – η 2 ‐H 2 BTEA) 2 ( μ 2 ‐H 2 BTEA) 2 (phen) 2 (NO 3 ) 2 ]⋅2CH 3 OH (Ln=Eu, Sm, Tb Or Dy; phen=1,10‐phenanthroline), and one trinuclear complex, [Cu 3 (BTBA) 3 (CH 3 OH) 4 ] . We merely explored their self‐assembly features, crystal structures, thermal stability, magnetic and fluorescence properties .…”

“…Consequently, our laboratory has already synthesized several complicated complexes bearing the acyl thiourea‐based carboxylate ligands, such as, two cluster polymers {[Cu I 6 Cu II 6 (BTEA) 6 (H 2 O) 3 (CH 3 OH) 6 ]⋅5H 2 O⋅3CH 3 OH} n (H 3 BTEA=2‐(3‐benzoylthioureido)ethanoic acid) and [Cu I 6 Cu II 6 (BTPA) 6 (H 2 O) 10 ] n (H 3 BTPA=2‐(3‐benzoylthioureido)propionic acid), and four dinuclear complexes [Ln 2 ( μ 2 – η 2 ‐H 2 BTEA) 2 ( μ 2 ‐H 2 BTEA) 2 (phen) 2 (NO 3 ) 2 ]⋅2CH 3 OH (Ln=Eu, Sm, Tb Or Dy; phen=1,10‐phenanthroline), and one trinuclear complex, [Cu 3 (BTBA) 3 (CH 3 OH) 4 ] . We merely explored their self‐assembly features, crystal structures, thermal stability, magnetic and fluorescence properties . Recently, with the in‐depth research on proton conduction of imidazole dicarboxylate‐based MOFs in our laboratory, above acyl thiourea carboxylate‐based complexes have appealed to our great attention again.…”

“…In order to further confirm the promoting role of ammonia and water molecules in such complexes, the research is required to be deepened in this field. So we herein firstly investigate the proton conductivities of two acyl thiourea carboxylated‐based complexes, a 2D cluster polymer, [Cu I 6 Cu II 6 (BTPA) 6 (H 2 O) 10 ] n ( 1 ) and a novel 0D cluster [Cu I 6 Cu II 6 (BTEA) 6 (H 2 O) 10 (DMF) 2 ]⋅6H 2 O ( 2 ) under water vapor. As a comparison, we further studied their proton conductivities under various concentrations of aqua‐ammonia vapors.…”

Solvothermal syntheses, crystal structure, and photoluminescent properties of two Cu(I) coordination polymers constructed by bisimidazole ligands

“…The choice of metal ions with various coordination geometry and ligands with different binding preference is generally of primary considerations [5][6][7][8]. The divalent copper ion is usually chosen as a center ion because its coordination number could vary from four to six, and it is easily deoxidized to monovalent copper ions under hydro(solvo)thermal synthesis conditions [9][10][11]. Aromatic polycarboxylic acids are versatile multidentate ligands to construct a variety of interesting structures [12][13][14].…”