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Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers

The hexatopic ligands 1,3,5-tris(4,2′:6′,4′′-terpyridin-4′-yl)benzene (1), 1,3,5-tris(3,2′:6′,3′′-terpyridin-4′-yl)benzene (2), 1,3,5-tris{4-(4,2′:6′,4′′-terpyridin-4′-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2′:6′,3′′-terpyridin-4′-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2′:6′,3′′-t...

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Autores principales: Manfroni, Giacomo, Prescimone, Alessandro, Constable, Edwin C., Housecroft, Catherine E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8764615/
https://www.ncbi.nlm.nih.gov/pubmed/35177954
http://dx.doi.org/10.1039/d1ce01531a
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author Manfroni, Giacomo
Prescimone, Alessandro
Constable, Edwin C.
Housecroft, Catherine E.
author_facet Manfroni, Giacomo
Prescimone, Alessandro
Constable, Edwin C.
Housecroft, Catherine E.
author_sort Manfroni, Giacomo
collection PubMed
description The hexatopic ligands 1,3,5-tris(4,2′:6′,4′′-terpyridin-4′-yl)benzene (1), 1,3,5-tris(3,2′:6′,3′′-terpyridin-4′-yl)benzene (2), 1,3,5-tris{4-(4,2′:6′,4′′-terpyridin-4′-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2′:6′,3′′-terpyridin-4′-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2′:6′,3′′-terpyridin-4′-yl)phenyl}benzene (5) have been prepared and characterized. The single crystal structure of 1·1.75DMF was determined; 1 exhibits a propeller-shaped geometry with each of the three 4,2′:6′,4′′-tpy domains being crystallographically independent. Packing of molecules of 1 is dominated by face-to-face π-stacking interactions which is consistent with the low solubility of 1 in common organic solvents. Reaction of 5 with [Cu(hfacac)(2)]·H(2)O (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) under conditions of crystal growth by layering resulted in the formation of [Cu(3)(hfacac)(6)(5)](n)·2.8nC(7)H(8)·0.4nCHCl(3). Single-crystal X-ray diffraction reveals an unusual 1D-coordination polymer consisting of a series of alternating single and double loops. Each of the three crystallographically independent Cu atoms is octahedrally sited with cis-arrangements two N-donors from two different ligands 1 and, therefore, cis-arrangements of coordinated [hfacac](−) ligands; this observation is unusual among compounds in the Cambridge Structural Database containing {Cu(hfacac)(2)N(2)} coordination units in which the two N-donors are in a non-chelating ligand.
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spelling pubmed-87646152022-02-15 Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers Manfroni, Giacomo Prescimone, Alessandro Constable, Edwin C. Housecroft, Catherine E. CrystEngComm Chemistry The hexatopic ligands 1,3,5-tris(4,2′:6′,4′′-terpyridin-4′-yl)benzene (1), 1,3,5-tris(3,2′:6′,3′′-terpyridin-4′-yl)benzene (2), 1,3,5-tris{4-(4,2′:6′,4′′-terpyridin-4′-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2′:6′,3′′-terpyridin-4′-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2′:6′,3′′-terpyridin-4′-yl)phenyl}benzene (5) have been prepared and characterized. The single crystal structure of 1·1.75DMF was determined; 1 exhibits a propeller-shaped geometry with each of the three 4,2′:6′,4′′-tpy domains being crystallographically independent. Packing of molecules of 1 is dominated by face-to-face π-stacking interactions which is consistent with the low solubility of 1 in common organic solvents. Reaction of 5 with [Cu(hfacac)(2)]·H(2)O (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) under conditions of crystal growth by layering resulted in the formation of [Cu(3)(hfacac)(6)(5)](n)·2.8nC(7)H(8)·0.4nCHCl(3). Single-crystal X-ray diffraction reveals an unusual 1D-coordination polymer consisting of a series of alternating single and double loops. Each of the three crystallographically independent Cu atoms is octahedrally sited with cis-arrangements two N-donors from two different ligands 1 and, therefore, cis-arrangements of coordinated [hfacac](−) ligands; this observation is unusual among compounds in the Cambridge Structural Database containing {Cu(hfacac)(2)N(2)} coordination units in which the two N-donors are in a non-chelating ligand. The Royal Society of Chemistry 2021-12-06 /pmc/articles/PMC8764615/ /pubmed/35177954 http://dx.doi.org/10.1039/d1ce01531a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Manfroni, Giacomo
Prescimone, Alessandro
Constable, Edwin C.
Housecroft, Catherine E.
Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
title Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
title_full Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
title_fullStr Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
title_full_unstemmed Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
title_short Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
title_sort stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8764615/
https://www.ncbi.nlm.nih.gov/pubmed/35177954
http://dx.doi.org/10.1039/d1ce01531a
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