6533b827fe1ef96bd1286f8b
RESEARCH PRODUCT
Metallophilic interactions in polymeric group 11 thiols
Kalle KolariMatti HaukkaVadim Yu. KukushkinJoona SahamiesAlexander S. NovikovElina Kaleniussubject
Crystallization of polymersInorganic chemistryProtonationAg010402 general chemistry01 natural sciencessymbols.namesakeTransition metalAuGeneral Materials ScienceVan der Waals radiusta116Cuchemistry.chemical_classification4-pyridinethiolmetallophilic interactions010405 organic chemistryLigandCationic polymerizationGeneral ChemistryCondensed Matter Physics0104 chemical sciencesCrystallographychemistryPolymerizationsymbolsCounteriondescription
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. peerReviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2016-10-01 | Solid State Sciences |