Metallophilic interactions in polymeric group 11 thiols |
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| Institution: | 1. University of Jyvaskyla, Department of Chemistry, P.O Box 35, FI-40014, University of Jyvaskyla, Finland;2. Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russian Federation;1. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016 (UP), India;2. DST Thematic Unit of Excellence on Soft Nanofabrication, Indian Institute of Technology Kanpur, Kanpur 208016 (UP), India;3. Center for Environmental Sciences and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016 (UP), India;1. Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India;2. Department of Chemistry, Howard University, Washington, DC 20059, USA;1. Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Lavrentieva St. 3, Novosibirsk, Russia;2. Novosibirsk State University, 630090 Pirogova St. 2, Novosibirsk, Russia;3. Skolkovo Institute of Science and Technology, Center for Electrochemical Energy Storage, 143026 Nobel St. 3, Moscow, Russia;4. Saint Petersburg State University, Institute of Chemistry, 199034 Universitetskaya Nab. 7-9, Saint Petersburg, Russia;5. Kazan Federal University, Alexander Butlerov Institute of Chemistry, Lobachevskogo Str. 1/29, 420008 Kazan, Russia;1. School of Physics and Materials Science, Shoolini University, Solan 173212, India;2. Department of Physics, Govt. G.M. Science College, Jammu 180006, India |
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| Abstract: | 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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| Keywords: | Cu Ag Au 4-pyridinethiol Metallophilic interactions |
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