Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/111768
Title: Lead(ii) Coordination Polymers Driven by Pyridine-Hydrazine Donors: From Anion-Guided Self-Assembly to Structural Features
Authors: Mahmoudi, G.
Afkhami, F. A.
Kennedy, A. R.
Zubkov, F. I.
Zangrando, E.
Kirillov, A. M.
Molins, E.
Mitoraj, M. P.
Safin, D. A.
Issue Date: 2020
Publisher: Royal Society of Chemistry
Royal Society of Chemistry (RSC)
Citation: Lead(ii) Coordination Polymers Driven by Pyridine-Hydrazine Donors: From Anion-Guided Self-Assembly to Structural Features / G. Mahmoudi, F. A. Afkhami, A. R. Kennedy et al. // Dalton Transactions. — 2020. — Vol. 49. — Iss. 32. — P. 11238-11248.
Abstract: 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.
Keywords: 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
URI: http://hdl.handle.net/10995/111768
Access: info:eu-repo/semantics/openAccess
SCOPUS ID: 85089710097
PURE ID: 13659213
ISSN: 1477-9226
metadata.dc.description.sponsorship: We are grateful to the University of Maragheh for the financial support of this research. The publication has been prepared with the support from the “RUDN University Program 5-100” (recipient F. I. Zubkov, synthesis of the ligands). DFT calculations were partially performed using the PL-Grid Infrastructure and resources provided by the ACC Cyfronet AGH (Cracow, Poland). A. M. Kirillov acknowledges the FCT and Portugal 2020 (LISBOA-01-0145-FEDER-029697 and UIDB/ 00100/2020). ICMAB acknowledges the Severo Ochoa Program (MINECO, SEV-2015-0496). M. P. Mitoraj acknowledges the financial support from the Polish National Science Center within the Sonata Bis Project 2017/26/E/ST4/00104.
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