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

Johnson, Magnus LU ; Džolić, Zoran ; Cetina, Mario ; Lahtinen, Manu ; Ahlquist, Mårten S G ; Rissanen, Kari ; Ohrström, Lars and Wendt, Ola LU (2013) In Dalton Transactions 42(23). p.8484-8491
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,... (More)
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 the solvent occurs and the hexagonal crystals transform into other non-porous polymorphs. Also by introducing a 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. (Less)
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author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
42
issue
23
pages
8484 - 8491
publisher
Royal Society of Chemistry
external identifiers
  • wos:000319286300040
  • pmid:23625006
  • scopus:84878081605
  • pmid:23625006
ISSN
1477-9234
DOI
10.1039/c3dt50190f
language
English
LU publication?
yes
id
9bb9f625-8fb6-4674-a859-59272f6de8b1 (old id 3733259)
date added to LUP
2016-04-01 10:27:53
date last changed
2022-01-25 23:31:47
@article{9bb9f625-8fb6-4674-a859-59272f6de8b1,
  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 the solvent occurs and the hexagonal crystals transform into other non-porous polymorphs. Also by introducing a 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.}},
  author       = {{Johnson, Magnus and Džolić, Zoran and Cetina, Mario and Lahtinen, Manu and Ahlquist, Mårten S G and Rissanen, Kari and Ohrström, Lars and Wendt, Ola}},
  issn         = {{1477-9234}},
  language     = {{eng}},
  number       = {{23}},
  pages        = {{8484--8491}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers.}},
  url          = {{http://dx.doi.org/10.1039/c3dt50190f}},
  doi          = {{10.1039/c3dt50190f}},
  volume       = {{42}},
  year         = {{2013}},
}