Interplay between the supramolecular motifs of polypyridyl metal complexes and halogen bond networks in cocrystals

Pfrunder, Michael C., Micallef, Aaron S., Rintoul, Llewellyn, Arnold, Dennis P. and McMurtrie, John (2016) Interplay between the supramolecular motifs of polypyridyl metal complexes and halogen bond networks in cocrystals. Crystal Growth and Design, 16 2: 681-695. doi:10.1021/acs.cgd.5b01211


Author Pfrunder, Michael C.
Micallef, Aaron S.
Rintoul, Llewellyn
Arnold, Dennis P.
McMurtrie, John
Title Interplay between the supramolecular motifs of polypyridyl metal complexes and halogen bond networks in cocrystals
Journal name Crystal Growth and Design   Check publisher's open access policy
ISSN 1528-7505
1528-7483
Publication date 2016-02-03
Year available 2016
Sub-type Article (original research)
DOI 10.1021/acs.cgd.5b01211
Open Access Status Not Open Access
Volume 16
Issue 2
Start page 681
End page 695
Total pages 15
Place of publication Washington, DC United States
Publisher American Chemical Society
Collection year 2017
Language eng
Formatted abstract
Combining [Ni(phen)3]I2 or [Ni(phen)3]Cl2 (phen = 1,10-phenanthroline) with the iodoperfluorobenzenes (IPFBs), 1,2-, 1,3-, 1,4-diiodotetrafluorobenzene (1,2-, 1,3-, and 1,4-DITFB, respectively), or 1,3,5-triiodotrifluorobenzene (1,3,5-TITFB) resulted in the formation of six different cocrystalline materials featuring halogen-bonded networks encapsulating [Ni(phen)3]2+ ions. The cocrystals have the general formula [Ni(phen)3][(IPFB)n(X2)(L)m]·solvate (n = 2 or 3; X = Cl– or I; L = halogen-bonded H2O and/or MeOH; solvate = isolated H2O and/or MeOH). The halide ions balance the charge of the metal complexes and simultaneously act as halogen bond acceptors for the electronically polarized iodine atoms of the IPFB donors. The structures display a wide variety of supramolecular motifs in the context of both the aggregation of the metal complexes and the topology and connectivity of the halogen bond networks. The well-known supramolecular “aryl embrace” motifs of [Ni(phen)3] complexes are present but are structurally compromised to varying degrees in the crystals of [Ni(phen)3][(1,2-DITFB)2I2]·MeOH, [Ni(phen)3][(1,3-DITFB)2I2]·2MeOH, and [Ni(phen)3][(1,3-DITFB)2(H2O)2Cl2]·1.5MeOH. In [Ni(phen)3][(1,3-DITFB)3I2], the [Ni(phen3]2+ complexes are so thoroughly enclosed in halogen-bonded networks that the metal complexes have no significant supramolecular contact. In contrast, in [Ni(phen)3][(1,4-DITFB)3I2(MeOH)0.5] and [Ni(phen)3][(1,3,5-TITFB)2Cl2] the complexes are arranged in typical aryl embrace motifs (pairwise and 1D chains, respectively), but with adjacent complexes held in closer proximity to each other than they reside in crystals of the pure metal complex. The interplay between the supramolecular chemistry of the halogen-bonded networks and the metal complexes was examined in detail, and the results demonstrate that it is possible to significantly influence the aggregation of metal complexes by encapsulation in different halogen bond networks.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 2 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 3 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Tue, 23 Feb 2016, 00:27:14 EST by System User on behalf of School of Chemistry & Molecular Biosciences