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Greasy tails switch 1D-coordination [Zn2(OAc)4(4'-(4-ROC6H4)-4,2':6',4''-tpy)]n polymers to discrete [Zn2(OAc)4(4'-(4-ROC6H4)-4,2':6',4''-tpy)2] complexes

Klein, Y. M. and Constable, E. C. and Housecroft, C. E. and Zampese, J. A. and Crochet, A.. (2014) Greasy tails switch 1D-coordination [Zn2(OAc)4(4'-(4-ROC6H4)-4,2':6',4''-tpy)]n polymers to discrete [Zn2(OAc)4(4'-(4-ROC6H4)-4,2':6',4''-tpy)2] complexes. CrystEngComm, 16 (42). pp. 9915-9929.

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Abstract

The homologous series of 4′-(4-ROC6H4)-4,2′:6′,4′′-tpy ligands with R = Me, Et, nPr, nBu, npentyl, nhexyl, nheptyl, noctyl, nnonyl and ndecyl (1–10, respectively) are reported, including single crystal structures of 6 and 7. Reactions of zinc(II) acetate with 1–10 have been investigated using room temperature crystallization methods (diffusion or layering). For ligands with the shortest alkoxy substituents, 1-dimensional coordination polymers [{Zn2(OAc)4(L)}n] (L = 1, 2 or 3) are formed. In each polymer, the 4′-(4-ROC6H4)-4,2′:6′,4′′-tpy ligands bind zinc through the two outer pyridine donors. The polymer structures are similar with the n-propyl chain adopting a folded conformation in [{Zn2(OAc)4(3)}n] which allows it to fit in the cavity occupied by methyl or ethyl groups in [{Zn2(OAc)4(1)}n] and [{Zn2(OAc)4(2)}n]. Reaction between 5 and Zn(OAc)2·2H2O gives both the coordination polymer [{2Zn2(OAc)4(5)·2H2O}n] and the discrete complex [Zn2(OAc)4(5)2]. Although the zig-zag form of the polymer chain in [{2Zn2(OAc)4(5)·2H2O}n] mimics those in [{Zn2(OAc)4(L)}n] (L = 1, 2 or 3), packing interactions differ and the wider separation of the chains in a sheet results in the incorporation of water molecules in the lattice. π-Stacking between pyridine rings in [{Zn2(OAc)4(L)}n] (L = 1, 2 or 3) produces infinite assemblies in contrast to isolated tetradecker π-stacks in [{2Zn2(OAc)4(5)·2H2O}n]. This assembly is replicated in [{4Zn2(OAc)4(7)·3H2O}n] (n-heptoxy substituents). In contrast, the n-hexoxy-containing coordination polymer crystallizes with acetic acid in the lattice; [{Zn2(OAc)4(6)·MeCO2H}n] consists of zig-zag polymer chains which π-stack in a manner which is unique among the other polymers. Further lengthening of the alkoxy chain favours the formation of [Zn2(OAc)4(L)2] (L = 8, 9 or 10) which are analogues of [Zn2(OAc)4(5)2]. In each, the 4′-(4-ROC6H4)-4,2′:6′,4′′-tpy ligand is monodentate. The alkoxy chains are in extended (or close to extended) conformations and pack into planar sheets with interdigitated chains. Pockets in the sheets are occupied by methyl groups of {Zn2(OAc)4} units in the adjacent sheet in a ball-and-socket assembly motif. The study shows that coordination polymers [{Zn2(OAc)4(L)}n] in which π-stacking are the dominant interactions are favoured for small alkoxy substituents (ligands 1–3); for ligands 8–10, discrete complexes [Zn2(OAc)4(L)2] in which van der Waals interactions dominate are observed. In the intermediate range (ligands 5–7), the preference between the two structure types appears to be marginal.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Klein, Maximilian and Zampese, Jennifer Ann
Item Type:Article, refereed
Article Subtype:Research Article
Bibsysno:Link to catalogue
Publisher:Royal Society of Chemistry
ISSN:1466-8033
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:31 Dec 2015 10:56
Deposited On:05 Dec 2014 09:45

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