Metal Ion Effects on Fullerene/Porphyrin Cocrystallization
Metal Ion Effects on Fullerene/Porphyrin Cocrystallization
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DOI：
10.1021/acs.cgd.9b01092
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发表时间：
2019-09
影响因子：
3.8
通讯作者：
Mrittika Roy;M. Olmstead;A. Balch
中科院分区：
文献类型：
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作者：
Mrittika Roy;M. Olmstead;A. Balch
本文系统地研究了以M=Co、Ni、Cu、Zn作为C60共结晶剂的后过渡金属八乙基卟啉MII(OEP)。在每种情况下，富勒烯都溶解在苯中，然后层叠在等摩尔的二氯甲烷卟啉溶液上。在CoII(OEP)和ZnII(OEP)体系中发现了一种新的柱状结构，其化学计量比为6：5。在这些共晶体中，一个富勒烯被两个卟啉包围，一个与一个卟啉相邻，而一个不与一个卟啉接触；然而，所有三个富勒烯在90K下都是有序的。更典型的，也是新的，具有CuII(OEP)和C60的1：1结构显示了背靠背的卟啉，所有八个乙基都拥抱了富勒烯。在这三种结构中，只有二氯甲烷作为溶剂。NiII(OEP)结构与NiII(OEP)·C60·2C6H6的已知结构有关，但含有约5%的二氯甲烷。在这些数字(OEP)/..
This investigation presents a systematic examination of the late transition metal octaethylporphyrins MII(OEP) with M = Co, Ni, Cu, and Zn as cocrystallization agents for C60. In each case, the fullerene was dissolved in benzene and then layered over an equimolar dichloromethane solution of the porphyrin. A striking new columnar structural type for these systems is found for CoII(OEP) and ZnII(OEP) with stoichiometric ratios 6:5 for porphyrin/fullerene. In these cocrystals, one fullerene is surrounded by two porphyrins, one is adjacent to only one porphyrin, while one makes no contact with a porphyrin; yet, all three fullerenes are ordered at 90 K. A more typical, also new, 1:1 structure with CuII(OEP) and C60 shows back-to-back porphyrins with all eight ethyl groups embracing the fullerene. In these three structures only dichloromethane is found as the solvate. The NiII(OEP) structure is related to the known structure of NiII(OEP)·C60·2C6H6 but has incorporated ca. 5% dichloromethane. In these NiII(OEP)/...