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. https://doi.org/10.1016/j.solidstatesciences.2016.08.005
Published inSolid State Sciences
DisciplineEpäorgaaninen ja analyyttinen kemiaOrgaaninen kemiaInorganic and Analytical ChemistryOrganic Chemistry
© 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. ...
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Related funder(s)Academy of Finland
Funding program(s)Research post as Academy Research Fellow, AoF; Research costs of Academy Research Fellow, AoF
Additional information about fundingFinancial support provided by the Magnus Ehrnrooth foundation (K.M) and Academy of Finland (M.H project no 139571, E.K project no's 284562 and 278743) as well as COST Action CM1302 are gratefully acknowledged. A.S.N is grateful to Russian Foundation for Basic Research for support (project No. 16-33-60063).
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