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金属卟啉：二聚体和三聚体。

Metalloporphines: Dimers and Trimers.

作者信息

Jentzen Walter, Shelnutt John A, Scheidt W Robert

机构信息

Fuel Science Department, Sandia National Laboratories , Albuquerque, New Mexico 87185-0710, United States.

Department of Chemistry, University of New Mexico , Albuquerque, New Mexico 87131, United States.

出版信息

Inorg Chem. 2016 Jun 20;55(12):6294-9. doi: 10.1021/acs.inorgchem.6b00956. Epub 2016 Jun 8.

DOI:10.1021/acs.inorgchem.6b00956
PMID:27276239
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4988798/
Abstract

Procedures for the purification and subsequent crystallization of the slightly soluble four-coordinate metallporphines, the simplest possible porphyrin derivatives, are described. Crystals of the porphine derivatives of cobalt(II), copper(II), platinum(II), and two polymorphs of zinc(II) were obtained. Analysis of the crystal and molecular structures shows that all except the platinum(II) derivative form an unusual trimeric species in the solid state. The isomorphous cobalt(II), copper(II), and one zinc(II) polymorph pack in the unit cell to form dimers as well as the trimers. Interplanar spacings between porphine rings are similar in both the dimers and trimers and range between 3.24 and 3.37 Å. Porphine rings are strongly overlapped with lateral shifts between ring centers in both the dimers and trimers with values between 1.52 and 1.70 Å or in Category S as originally defined by Scheidt and Lee. Periodic trends in the M-Np bond distances parallel those observed previously for tetraphenyl- and octaethylporphyrin derivatives.

摘要

本文描述了微溶性四配位金属卟啉（最简单的卟啉衍生物）的纯化及后续结晶过程。获得了钴（II）、铜（II）、铂（II）的卟啉衍生物晶体以及锌（II）的两种多晶型物晶体。晶体和分子结构分析表明，除铂（II）衍生物外，所有物质在固态下均形成一种不寻常的三聚体物种。同构的钴（II）、铜（II）和一种锌（II）多晶型物在晶胞中堆积形成二聚体以及三聚体。二聚体和三聚体中卟啉环之间的面间距相似，范围在3.24至3.37 Å之间。在二聚体和三聚体中，卟啉环强烈重叠，环中心之间的侧向位移值在1.52至1.70 Å之间，或属于Scheidt和Lee最初定义的S类。M-Np键距离的周期性趋势与先前在四苯基和八乙基卟啉衍生物中观察到的趋势相似。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/6b48d68e16d1/nihms809769f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/bc0646e31258/nihms809769f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/3a27f5753eb6/nihms809769f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/d4c09e601361/nihms809769f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/6b48d68e16d1/nihms809769f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/bc0646e31258/nihms809769f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/3a27f5753eb6/nihms809769f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/d4c09e601361/nihms809769f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/305b/4988798/6b48d68e16d1/nihms809769f4.jpg

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本文引用的文献

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Direct synthesis of magnesium porphine via 1-formyldipyrromethane.通过1-甲酰基二吡咯甲烷直接合成镁卟啉。
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