Supramolecular lead(ii) architectures engineered by tetrel bonds

In this work, we have directed our attention to the evaluation of closely related bis-pyridyl ligands N′-(pyridin-2-ylmethylene)picolinohydrazide (HLI), N′-(pyridin-2-ylmethylene)nicotinohydrazide (HLII) and N′-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide (HLIII) as linkers for PbII extended structures. The reaction of Pb(NO3)2 or Pb(ClO4)2 with an equimolar amount of HLI-III in the presence of KSCN in EtOH at 60 °C leads to the formation of heteroleptic coordination polymers [Pb(HLI)(NO3)2]n, [Pb(LII)(ClO4)]n and [Pb(HLIII)(NO3)(NCS)]n. The structures of all these complexes are highly dictated by both the structure of the parent organic ligand and the nature of inorganic anions. In all cases, the main structural motif is a zig-zag 1D coordination polymer, which can be further extended to higher dimensions due to tetrel bonds, N-H⋯O hydrogen bonds and π⋯π interactions. The formation of tetrel bonds was possible thanks to a hemidirected coordination sphere of the PbII atoms in all the described complexes. As a result, the overall coordination number of the metal center was found to be 10, 7 and 8 in [Pb(HLI)(NO3)2]n, [Pb(LII)(ClO4)]n and [Pb(HLIII)(NO3)(NCS)]n, respectively. DFT calculations were performed in order to determine the nature of non-covalent interactions and stability of the obtained structures. This journal is © The Royal Society of Chemistry.

Akbari Afkhami F. , Mahmoudi G. 2 , Qu F.1 , Gupta A.1 , Köse M.3 , Zangrando E.4 , Zubkov F.I. 5 , Alkorta I.6 , Safin D.A.7, 8, 9
Royal Society of Chemistry
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  • 1 Department of Chemistry, University of Alabama, Box 870336 250 Hackberry Lane, Tuscaloosa, AL 35487, United States
  • 2 Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
  • 3 Chemistry Department, Kahramanmaraş Sütçü Imam University, Kahmaranmaraş, 46050, Turkey
  • 4 Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, Trieste, 34127, Italy
  • 5 Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia, RUDN University, 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
  • 6 Instituto de Quimica Medica, Juan de la Cierva 3, 28006-Madrid, Spain
  • 7 University of Tyumen, Volodarskogo Str. 6, Tyumen, 625003, Russian Federation
  • 8 West-Siberian Interregional Scientific and Educational Center, Russian Federation
  • 9 Innovation Center for Chemical and Pharmaceutical Technologies, Ural Federal University Named after the First President of Russia B.N. Eltsin, Mira Str. 19, Ekaterinburg, 620002, Russian Federation
Ключевые слова
Chlorine compounds; Hydrogen bonds; Ligands; Polymers; 1D coordination polymer; Coordination number; Coordination Polymers; Coordination sphere; Extended structures; Higher dimensions; Non-covalent interaction; Structural motifs; Lead compounds
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