Two unique antiferromagnetic 3D frameworks with unusual CuII4 cluster and alternate CuII4 + CuII1 structural motif tuned by aromatic polycarboxylate coligand

Abstract

Two new 3-amino-1,2,4-triazole (amtrz)-based 3D MOFs, [Cu 4 (amtrz) 2 (m 3 -OH) 2 (btc) 2 ] n (1), and [Cu 5 (amtrz) 2 (H 2 O) 2 (m 3 -OH) 2 (btec) 2 ] n (2) (btc 3À ¼ 1,3,5-benzenetricarboxylate and btec 4À ¼ 1,2,4,5benzenetetracarboxylate), were hydrothermally synthesized and structurally and magnetically characterized. Each cationic [Cu 4 (amtrz) 2 (m 3 -OH) 2 ] 6+ cluster in 1 is periodically extended into an infinite 3,6-connected rtl-type topological network via six btc 3À ligands. In contrast, analogous Cu II 4 clusters to 1 and square-planar Cu II 1 cores in 2 are alternately interlinked through btec 4À linkers to generate a 3D

Structures and magnetic properties of mixed triazolyl-aromatic polycarboxylate-based metal complexes

“…当芳香酸羧基表现出多种连接模式时, 可以与 三唑及羟基阴离子协同配位构造出具有复杂混桥模 式的核簇结构(图 4). 如图 4(a)所示, 4 个铜(II)离子被 [28,34] . 在四核簇中, 羧基表现出 2.11 及 2.20 两种配位桥连模式.…”

“…去质子的芳香多羧酸配体不仅通过羧基的不同 配位模式影响核簇的构建, 而且研究发现, 在核簇连 图 3 三核金属簇子结构 [29,33,37] 图 4 羧基与三唑协同配位构造的四核及五核金属簇子结 构 [20,28,29,34]…”

Three complexes of manganese(II) based on a new semirigid tetracarboxylate and N-containing ligands: Synthesis, crystal structures and magnetic properties

“…(ii) The carboxylate groups can deprotonate completely or partially in order to meet the needs of coordination for different metal ions. (iii) The carboxylic groups can mediate magnetic coupling by bridging metal ions with the syn-syn bonding mode [14][15][16]. For example, 4,4 0 -oxidiphthalic acid [17] and 2,2 0 ,3,3 0 -oxydiphthalic acid [18], a kind of semirigid multicarboxylate ligand in which two benzene rings are bridged by an O atom, have been employed widely to construct interesting structures.…”

Two highly connected frameworks and one polythreading architecture based on multidentate N-donor ligands: Syntheses, structures, characterizations and photoluminescent properties

“…However, the construction of these kinds of CPs remains a challenge, because the construction of CPs is mainly dependent on the combination of several factors, such as the organic ligands, solvents, pH values, temperatures and metal atoms [17][18][19]. Among these, the organic anions play crucial roles in the construction of CPs because of their coordination and structure directing roles [20]. In this regard, aromatic multicarboxylic ligands, such as 1,3,5-benzenetricarboxylic acid (H 3 btc) and 1,2,4,5-benzenetetracarboxylic acid (H 4 btec), as an important type of organic anions, have been extensively used as multifunctional organic linkers for the construction of CPs [20][21][22][23][24].…”

“…Among these, the organic anions play crucial roles in the construction of CPs because of their coordination and structure directing roles [20]. In this regard, aromatic multicarboxylic ligands, such as 1,3,5-benzenetricarboxylic acid (H 3 btc) and 1,2,4,5-benzenetetracarboxylic acid (H 4 btec), as an important type of organic anions, have been extensively used as multifunctional organic linkers for the construction of CPs [20][21][22][23][24]. H 3 btc and H 4 btec have been proven to be powerful organic ligands, due to their high symmetries and various coordination modes leading to the formation of diverse CPs with fascinating structures, such as highly connected and entangled systems [25][26][27][28][29][30][31][32].…”