Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Inorg Chem. 2011 Dec 19;50(24):12739-46. doi: 10.1021/ic2018715. Epub 2011 Nov 15.
Synthesized and structurally characterized is a new series of soft-host frameworks assembled by charge-assisted hydrogen bonds between an anionic metal complex (MC) and cationic organic linkers (OL), specifically Co(en)(ox)(2) and diprotonated 4,4'-bipyridinium (H(2)bpy) or 1,2-bis(4-pyridinium)ethylene (H(2)bpye). While frameworks built of cationic complexes and anionic organic linkers are already well-known, the seven new compounds described here represent the first series of frameworks with reversed polarity, that is, made of anionic complexes and cationic organic linkers. The compounds have a general formula [OL]MC·n(guest), where the guest molecules 4,4'-biphenol (bp), 4-methoxyphenol (mp), 1,4-dimethoxybenzene (dmb), 1,6-dimethoxynaphtalene (dmn), and 4-nitroanisole (na). Structurally the compounds can be described as pillared-layer frameworks with layers constructed of MC anions and linked together by hydrogen-bonded cationic OL pillars. The guest molecules occupy the galleries between the pillars while their steric, electronic, and π-π and hydrogen-bonding capabilities influence the overall structure of the soft frameworks.
合成并结构表征了一系列由带负电荷的金属配合物（MC）和带正电荷的有机连接体（OL）之间的电荷辅助氢键组装而成的新型软骨架框架，具体为[Co(en)(ox)(2)]-和二质子化 4,4'-联吡啶（H2bpy）或 1,2-双（4-吡啶基）乙烯（H2bpye）。虽然由阳离子配合物和阴离子有机连接体构建的骨架已经为人熟知，但这里描述的七个新化合物代表了第一个具有反转极性的骨架系列，即由阴离子配合物和阳离子有机连接体组成。这些化合物具有通式[OL][MC]2·n(guest)，其中客体分子为 4,4'-联苯酚(bp)、4-甲氧基苯酚(mp)、1,4-二甲氧基苯(dmb)、1,6-二甲氧基萘(dmn)和 4-硝基苯甲醚(na)。在结构上，这些化合物可以描述为由 MC 阴离子构建的层状骨架，这些层由氢键连接的阳离子 OL 支柱连接在一起。客体分子占据支柱之间的通道，而它们的空间、电子和π-π和氢键能力影响软骨架的整体结构。
