Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)

The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyrid...

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Main Authors:	Giacomo Manfroni, Simona S. Capomolla, Alessandro Prescimone, Edwin C. Constable, Catherine E. Housecroft
Format:	Article
Language:	English
Published:	MDPI AG 2021-07-01
Series:	Inorganics
Subjects:	copper 4,2′:6′,4″-terpyridine 3,2′:6′,3″-terpyridine coordination polymer isomers
Online Access:	https://www.mdpi.com/2304-6740/9/7/54

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author	Giacomo Manfroni Simona S. Capomolla Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft
author_facet	Giacomo Manfroni Simona S. Capomolla Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft
author_sort	Giacomo Manfroni
collection	DOAJ
description	The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (<b>1</b>), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (<b>2</b>), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (<b>3</b>), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (<b>4</b>) have been prepared and characterized. The single crystal structures of <b>1</b> and <b>2</b> were determined. The 1D-polymers [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>1</b>)<sub>2</sub>]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)<sub>2</sub>(<b>2</b>)]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>5</sub>Me, [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub>, [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl, and [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl have been formed by reactions of <b>1</b>, <b>2</b>, <b>3</b> and <b>4</b> with [Cu(hfacac)<sub>2</sub>]·H<sub>2</sub>O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>1</b>)<sub>2</sub>]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> and [Cu(hfacac)<sub>2</sub>(<b>2</b>)]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>5</sub>Me are zig-zag chains and the different substitution position of the CF<sub>3</sub> group in <b>1</b> and <b>2</b> does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> and [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl, the peripheral 3-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub> unit is accommodated in a pocket between two {Cu(hfacac)<sub>2</sub>} units and engages in four C–H<sub>phenyl</sub>...F–C<sub>hfacac</sub> contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> and [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating <b>1</b> and <b>2</b>. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands <b>3</b> or <b>4</b>.
first_indexed	2024-03-10T09:36:24Z
format	Article
id	doaj.art-8a50204b9f594bf7a5be7521bd564433
institution	Directory Open Access Journal
issn	2304-6740
language	English
last_indexed	2024-03-10T09:36:24Z
publishDate	2021-07-01
publisher	MDPI AG
record_format	Article
series	Inorganics
spelling	doaj.art-8a50204b9f594bf7a5be7521bd5644332023-11-22T04:04:07ZengMDPI AGInorganics2304-67402021-07-01975410.3390/inorganics9070054Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)Giacomo Manfroni0Simona S. Capomolla1Alessandro Prescimone2Edwin C. Constable3Catherine E. Housecroft4Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandDepartment of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, SwitzerlandThe isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (<b>1</b>), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (<b>2</b>), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (<b>3</b>), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (<b>4</b>) have been prepared and characterized. The single crystal structures of <b>1</b> and <b>2</b> were determined. The 1D-polymers [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>1</b>)<sub>2</sub>]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)<sub>2</sub>(<b>2</b>)]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>5</sub>Me, [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub>, [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl, and [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl have been formed by reactions of <b>1</b>, <b>2</b>, <b>3</b> and <b>4</b> with [Cu(hfacac)<sub>2</sub>]·H<sub>2</sub>O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>1</b>)<sub>2</sub>]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> and [Cu(hfacac)<sub>2</sub>(<b>2</b>)]<i><sub>n</sub></i>·2<i>n</i>C<sub>6</sub>H<sub>5</sub>Me are zig-zag chains and the different substitution position of the CF<sub>3</sub> group in <b>1</b> and <b>2</b> does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> and [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl, the peripheral 3-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub> unit is accommodated in a pocket between two {Cu(hfacac)<sub>2</sub>} units and engages in four C–H<sub>phenyl</sub>...F–C<sub>hfacac</sub> contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu<sub>2</sub>(hfacac)<sub>4</sub>(<b>3</b>)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> and [Cu(hfacac)<sub>2</sub>(<b>4</b>)]<i><sub>n</sub></i>·<i>n</i>C<sub>6</sub>H<sub>5</sub>Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating <b>1</b> and <b>2</b>. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands <b>3</b> or <b>4</b>.https://www.mdpi.com/2304-6740/9/7/54copper4,2′:6′,4″-terpyridine3,2′:6′,3″-terpyridinecoordination polymerisomers
spellingShingle	Giacomo Manfroni Simona S. Capomolla Alessandro Prescimone Edwin C. Constable Catherine E. Housecroft Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione) Inorganics copper 4,2′:6′,4″-terpyridine 3,2′:6′,3″-terpyridine coordination polymer isomers
title	Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)
title_full	Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)
title_fullStr	Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)
title_full_unstemmed	Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)
title_short	Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)
title_sort	isomeric 4 2 6 4 and 3 2 6 3 terpyridines with isomeric 4 trifluoromethylphenyl substituents effects on the assembly of coordination polymers with cu hfacac sub 2 sub hhfacac hexafluoropentane 2 4 dione
topic	copper 4,2′:6′,4″-terpyridine 3,2′:6′,3″-terpyridine coordination polymer isomers
url	https://www.mdpi.com/2304-6740/9/7/54
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Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)<sub>2</sub>] (Hhfacac = Hexafluoropentane-2,4-dione)

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