原位羟基化2,2′-联吡啶类配体及其新颖的铜(Ⅰ)和混价铜(I,Ⅱ)超分子构筑的合成

本文利用水热法合成了两个新型一价铜配合物Cu2(ophen)2]·H2O的类同质多晶结构(1a和1β)和一个混合价的铜配合物Cu2(obpy)2(NO3)·H2O(2).晶体结构分析表明:1a显现出于无水的类似物Cu2(ophen)2]相同的堆积方式,1β则形成出新奇的空间堆积.混合价化合物2是完全离域的,通过氢键集聚体(H2O)2(NO3-)2]将两个Cu2(obpy)2]+单元连接起来形成哑铃状的四核结构.

In Situ Hydroxylated 2,2′-bipyridine-like Ligands and Their New Cu(I)and Cu(Ⅰ,H)Supramolecular Architectures

Two new pseudo-polymorphs Cu I2(ophen)2]·2H2O(1ot and 1β)of the trimorphic Cu I2(ophen)2](Hophen=1H-1,10]phenanthrolin-2-one),as well as a mixed-valent copper(Ⅰ ,Ⅱ)complex Cu2(obpy)2(NO3)]· H2O(2)(Hobpy=lH-2,2′]bipyridinyl-6-one)were hydrothermally prepared at 130～140 ℃. 1β possesses a new molecular packing pattern of the planar Cu I 2(ophen)2] molecules,whereas that of its supramolecular isomer 1ot is identical to that ofβ-Cu I 2(ophen)2]. In 2,a new hydrogen-bonded aggregate (H2O)2(NO3-)2] links two Cu2(obpy)2]+ moieties to form the dumbbell-like structure similar to the dicarboxylate-linked tetranulear analogues described previously,in which the valence of the copper atoms is delocalized. CCDC: 247025～247027.