Lead(ii) coordination polymers driven by pyridine-hydrazine donors: From anion-guided self-assembly to structural features

In this work, we report extensive experimental and theoretical investigations on a new series of PbII coordination polymers exhibiting extended supramolecular architectures, namely [Pb2(LI)(NCS)4]n (1), [Pb(HLII)I2]n (2), [Pb(LIII)I]n (3) and [Pb(HLIV)(NO3)2]n·nMeOH (4), which were self-assembled from different PbII salts and various pyridine-hydrazine based linkers, namely 1,2-bis(pyridin-3-ylmethylene)hydrazine (LI), (pyridin-4-ylmethylene)isonicotinohydrazide (HLII), 1-(pyridin-2-yl)ethylidenenicotinohydrazide (HLIII) and phenyl(pyridin-2-yl)methylenenicotinohydrazide (HLIV), respectively. It is recognized that the origin of self-assembling is fundamentally rooted in a dual donor (6s2/6p0 hybridized lone electron pair) and electrophilic behaviour of PbII. This allows production of extended topologies from a 1D polymeric chain in 4 through a 2D layer in 2 to the 3D frameworks in 1 and 3, predominantly due to the cooperative action of both covalent and non-covalent tetrel interactions of the overall type Pb-X (X = O, N, S, I). Counterintuitively, the latter, seemingly weak interactions, have appeared to be even stronger than the typical covalent bonds due to the presence of a bunch of supportive London dispersion dominated contacts: π⋯π, Lp⋯π, C-H⋯O, C-H⋯I, C-H⋯H-C as well as more typical mainly electrostatically driven N-H⋯O or N/O-H⋯O hydrogen bonds. It is revealed that the constituting generally strong tetrel type Pb-X (X = O, N, S, I) bonds, though dominated by a classic Coulomb term, are therefore characterized by a very important London dispersion constituent, extremely strong relativistic effects and the two way dative-covalent Pb ↔ X electron charge delocalization contribution as revealed by the Extended Transition State Natural Orbital for Chemical Valence (ETS-NOCV) charge and energy decomposition scheme. It unravels that the pyridine-hydrazine linkers are also excellent London dispersion donors, and that together with the donor-acceptor properties of the heavy (relativistic) PbII atoms and nucleophilic counterions lead to extended self-assembling of 1-4. © 2020 The Royal Society of Chemistry.

Mahmoudi G. 1 , Afkhami F.A.2 , Kennedy A.R.3 , Zubkov F.I. 4 , Zangrando E.5 , Kirillov A.M. 6 , Molins E.7 , Mitoraj M.P.8 , Safin D.A.9, 10, 11
Royal Society of Chemistry
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  • 1 Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
  • 2 Department of Chemistry, University of Alabama, Box 870336 250 Hackberry Lane, Tuscaloosa, AL 35487, United States
  • 3 Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow Scotland, G1 1XL, United Kingdom
  • 4 Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia, RUDN University, Miklukho-Maklaya Str. 6, Moscow, 117198, Russian Federation
  • 5 Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, Trieste, 34127, Italy
  • 6 Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisboa, 1049-001, Portugal
  • 7 Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus de la Universitat Autònoma de Barcelona, Bellaterra, 08193, Spain
  • 8 Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, Cracow, 30-387, Poland
  • 9 University of Tyumen, Volodarskogo Str. 6, Tyumen, 625003, Russian Federation
  • 10 West-Siberian Interregional Scientific and Educational Center, Russian Federation
  • 11 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
Atoms; D region; Dispersions; Hydrazine; Hydrogen bonds; Negative ions; Polymers; Pyridine; Self assembly; Coordination Polymers; Donor-acceptor properties; Electrostatically driven; Energy decomposition; Guided self-assembly; Nucleophilic counterions; Supramolecular architectures; Theoretical investigations; Lead compounds
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