Chemical reaction-inspired crystal growth of a coordination polymer toward morphology design and control
Chemical reaction-inspired crystal growth of a coordination polymer toward morphology design and control
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DOI：
10.1021/ja065254k
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发表时间：
2006-12-13
影响因子：
15
通讯作者：
Kitagawa, Susumu
中科院分区：
文献类型：
--
作者：
Masaoka, Shigeyuki;Tanaka, Daisuke;Kitagawa, Susumu
本文报道了一种新的配合物{[Cu-3（CN）（3）{hat（CN）（3）（OEt）（3）}]}n（1）（hat-（CN）（3）（OEt）（3））2，6，10-三氰基-3，7，11-三乙氧基-1，4，5，8，9，12-六氮杂苯并菲）晶体生长体系。该配位聚合物通过2，3，6，7，10，11-六氰基-1，4，5，8，9，12-六氮杂苯并菲（hat-（CN）（6））、乙醇和铜（I）配合物的反应结晶，涉及共价键的断裂和形成。在本系统中获得的晶体形态包含哑铃，齿轮，和超晶格。此外，在垂直于c轴的生长中，观察到规则间隔的周期性分支，从而提供超晶格形态。对哑铃晶体生长的观察表明，平行于和垂直于晶体学c轴的生长速率有很大的不同：前者随反应时间的延长而急剧变化，而后者几乎不变。这些结果被再现为一个简单的反应扩散系统，表明晶体表面上的化学反应在确定宏观晶体形态中起着重要的作用。
This paper reports a novel crystal growth system of a coordination framework {[Cu-3(CN)(3){hat(CN)(3)(OEt)(3)}]}n (1) (hat-(CN)(3)(OEt)(3)) 2,6,10-tricyano-3,7,11-triethoxy-1,4,5,8,9,12-hexaazatriphenylene). The coordination polymer is crystallized through the reaction of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12hexaazatriphenylene (hat-(CN)(6)), ethanol, and copper(I) complex, involving the breaking and forming of covalent bonds. The crystal morphologies obtained in the present system contain dumbbells, cogwheels, and superlattices. Moreover, in the growth perpendicular to the c-axis, periodic ramification at regular interval is observed, affording superlattice morphologies. Observation of the growth of dumbbell crystals shows that the growth rates parallel and perpendicular to the crystallographic c-axis are quite different: the former shows a drastic change with the reaction duration, while the latter is almost constant. These results are reproduced as a simple reaction-diffusion system, indicating that chemical reactions on crystal surfaces play an important role in determining the macroscopic crystal morphologies.