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通过取代效应和构象柔性 3,2':6',3"-三联吡啶来适应（4,4）网络。

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2':6',3"-Terpyridines.

机构信息

Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland.

出版信息

Molecules. 2021 Oct 20;26(21):6337. doi: 10.3390/molecules26216337.

DOI:10.3390/molecules26216337
PMID:34770746
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8587907/
Abstract

Coordination networks formed between Co(NCS) and 4'-substituted-[1,1'-biphenyl]-4-yl-3,2':6',3"-terpyridines in which the 4'-group is Me (), H (), F (), Cl () or Br () are reported. [Co()(NCS)]·4.5CHCl, [Co()(NCS)]·4.3CHCl, [Co()(NCS)]·4CHCl, [Co()(NCS)], and [Co()(NCS)]·CHCl are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2':6',3"-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co()(NCS)]·4.5CHCl, [Co()(NCS)]·4.3CHCl, [Co()(NCS)]·4CHCl, cone-like arrangements of [1,1'-biphenyl]-4-yl units pack through pyridine…arene π-stacking, whereas Cl…π interactions are dominant in the packing in [Co()(NCS)] The introduction of the Br substituent in ligand switches off both face-to-face π-stacking and halogen…π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers - are structurally similar and the lattice accommodates CHCl molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co()(NCS)]·4CHCl can be reversibly removed.

摘要

报道了 Co(NCS) 与 4'-取代-[1,1'-联苯]-4-基-3,2':6',3"-三联吡啶之间形成的配位网络，其中 4'-基团为 Me (), H (), F (), Cl () 或 Br ()。[Co()(NCS)]·4.5CHCl、[Co()(NCS)]·4.3CHCl、[Co()(NCS)]·4CHCl、[Co()(NCS)] 和 [Co()(NCS)]·CHCl 是由 4-连接钴节点导向的 2D 网络。3,2':6',3"-三联吡啶单元构象的变化与不同的外围取代基相结合，导致了三种结构类型。在 [Co()(NCS)]·4.5CHCl、[Co()(NCS)]·4.3CHCl、[Co()(NCS)]·4CHCl 中，[1,1'-联苯]-4-基单元通过吡啶…芳烃π堆积形成锥形排列，而在 [Co()(NCS)]中，Cl…π相互作用占主导地位。配体中引入 Br 取代基会同时关闭面对面的π堆积和卤素…π相互作用，并且包装相互作用受到更微妙的控制。具有有机连接体的组装体 - 在结构上相似，晶格在不同的腔室中容纳 CHCl 分子；热重分析证实 [Co()(NCS)]·4CHCl 中有一半的溶剂可以可逆地去除。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/0a04c8afb55d/molecules-26-06337-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/2f39c8a841c7/molecules-26-06337-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/8883fed10468/molecules-26-06337-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/a164b02175ec/molecules-26-06337-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/8641c7b4d0c1/molecules-26-06337-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/9de79000ce41/molecules-26-06337-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/132905a4a272/molecules-26-06337-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/4598e9124b86/molecules-26-06337-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/972a0f36f381/molecules-26-06337-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/a629f3746762/molecules-26-06337-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/e60cb2063de1/molecules-26-06337-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/82d358e270cd/molecules-26-06337-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/e09db9e0941a/molecules-26-06337-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/0a04c8afb55d/molecules-26-06337-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/2f39c8a841c7/molecules-26-06337-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/8883fed10468/molecules-26-06337-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/a164b02175ec/molecules-26-06337-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/8641c7b4d0c1/molecules-26-06337-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/9de79000ce41/molecules-26-06337-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/132905a4a272/molecules-26-06337-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/4598e9124b86/molecules-26-06337-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/972a0f36f381/molecules-26-06337-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/a629f3746762/molecules-26-06337-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/e60cb2063de1/molecules-26-06337-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/82d358e270cd/molecules-26-06337-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/e09db9e0941a/molecules-26-06337-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4bd/8587907/0a04c8afb55d/molecules-26-06337-g010.jpg

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