Metallophilic interactions in polymeric group 11 thiols
Kolari, K., Sahamies, J., Kalenius, E., Novikov, A. S., Kukushkin, V. Y., & Haukka, M. (2016). Metallophilic interactions in polymeric group 11 thiols. Solid State Sciences, 60 (October), 92-98. doi:10.1016/j.solidstatesciences.2016.08.005
Published inSolid State Sciences
© 2016 Elsevier Masson SAS. This is a final draft version of an article whose final and definitive form has been published by Elsevier. Published in this repository with the kind permission of the publisher.
Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2− counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 are linear. The protonation level of the thiol ligand had an impact on the crystallization of polymers. Both nature of the metal center and reaction conditions affected the polymerization. QTAIM analysis confirmed direct metal-metal contacts only in polymers 1 and 3. In polymer 2, no theoretical evidence of argentophilic contacts was obtained even though the Ag⋅⋅⋅Ag distance was found to be less than sum of the Bondi's van der Waals radius of silver. ...