Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers
Artikel i vetenskaplig tidskrift, 2013

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-butyl-phosphino)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.


M. T. Johnson

Jyväskylän Yliopisto

Lunds universitet

Z. Dzolic

Institute Ruder Boskovic

Jyväskylän Yliopisto

M. Cetina

Sveučilište u Zagrebu

Jyväskylän Yliopisto

M. Lahtinen

Jyväskylän Yliopisto

M. S. G. Ahlquist

Kungliga Tekniska Högskolan (KTH)

K. Rissanen

Jyväskylän Yliopisto

Lars Öhrström

Chalmers, Kemi- och bioteknik, Fysikalisk kemi

O. F. Wendt

Lunds universitet

Dalton Transactions

1477-9226 (ISSN) 1477-9234 (eISSN)

Vol. 42 8484-8491


Oorganisk kemi