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Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers

Johnson, Magnus T.; Džolić, Zoran; Cetina, Mario; Lahtinen, Manu; Ahlquist, Mårten S.G.; Rissanen, Kari; Öhrström, Lars; Wendt, Ola F. (2013) Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers. Dalton transactions, 42 (23). pp. 8484-8491. ISSN 1477-9226

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Abstract

Understanding the mechanism by which advanced materials assemble is essential for the design of new materials with desired properties. Here, we report a method to form chiral, potentially porous materials through spontaneous resolution of conformers of a PCP pincer palladium complex ({; ; 2, 6-bis[(di-t-butylphosphino)methyl]phenyl}; ; palladium(II)halide). The crystallisation is controlled by weak hydrogen bonding giving rise to chiral qtz-nets and channel structures, as shown by 16 such crystal structures for X = Cl, and Br with various solvents like pentane and bromobutane. The fourth ligand (in addition to the pincer ligand) on palladium plays a crucial role ; the chloride and the bromide primarily form hexagonal crystals with large 1D channels, whereas the iodide (presumably due to its inferior hydrogen bonding capacity) forms monoclinic crystals without channels. The hexagonal channels are completely hydrophobic and filled with disordered solvent molecules. Upon heating loss of solvent occurs and the hexagonal crystals transform into other non-porous polymorphs. Also by introducing strong acid, the crystallisation process can be directed to a different course, giving several different non-porous polymorphs. In conclusion a number of rules can be formulated dictating the formation of hexagonal channel structures based on pincer palladium complexes. Such rules are important for a rational design of future self-assembling materials with applications in storage and molecular recognition.

Item Type: Article
Uncontrolled Keywords: palladium pincer complexes ; hexagonal channels ; self-assembly ; weak interactions
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Organic Chemistry and Biochemistry
Depositing User: Sofija Konjević
Date Deposited: 07 May 2015 14:13
Last Modified: 07 May 2015 14:13
URI: http://fulir.irb.hr/id/eprint/1909
DOI: 10.1039/c3dt50190f

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