Research output: Contribution to journal › Article › peer-review
Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Tetrel bonding stabilization of a new coordination polymer constructed from lead(ii) azide and 1-(pyridin-2-yl)ethylidenepicolinohydrazide
AU - Mahmoudi, Ghodrat
AU - Zangrando, Ennio
AU - Gurbanov, Atash
AU - Eftekhari-Sis, Bagher
AU - Mitoraj, Mariusz
AU - Sagan, Filip
AU - Safin, Damir
N1 - This work was supported by the Fundação para a Ciência e a Tecnologia (FCT), project UIDB/00100/2020 of Centro de Química Estrutural. A. V. Gurbanov acknowledges the FCT and Instituto Superior Técnico (DL 57/2016 and L 57/2017 Program, Contract no.: IST-ID/110/2018). M. P. Mitoraj and F. Sagan acknowledge Poland's high-performance Infrastructure PLGrid (HPC Centers: ACK Cyfronet AGH, PCSS, CI TASK, WCSS) for providing computer facilities.
PY - 2023
Y1 - 2023
N2 - In this work we report a new PbII coordination polymer [Pb3L2(N3)4]n, which was obtained from Pb(N3)2 and 1-(pyridin-2-yl)ethylidenepicolinohydrazide (HL). The complex exhibits a 1D polymeric chain, constructed from the {[Pb3(N3)4]2+}n backbone, decorated with deprotonated organic L− ligands. The latter ligands are pentadentate and link two metal cations. The PbII ions were found to be in a N5O or N5O2 coordination environment, formed by covalent bonds. The azide ligands either bind four metals in a μ4-1,1,3,3 coordination mode or are coordinated to metal centers as terminal ligands. All the metal centers exhibit a hemidirected coordination geometry with a pronounced coordination gap, which allows the close approach of an additional nitrogen atom arising from an adjacent terminal azide ligand. A simplified underlying network of [Pb3L2(N3)4]n, without considering Pb⋯N tetrel bonds, exhibits the tetranodal 3,4,4,4-connected chain topology, while considering all Pb⋯N tetrel bonds, the binodal 4,5-connected chain topology was shown. The crystal packing of [Pb3L2(N3)4]n is reinforced by intermolecular π⋯π stacking interactions, formed by PbII-based five-membered chelate metallocycles and pyridine rings. In-depth bonding analysis using ETS-NOCV, IQA and NCI methods demonstrates that although the azide anions experience significant steric crowding due to repulsive azide-azide interactions, they are engaged in strong attractive, Coulomb dominated, dative-covalent Pb-N and tetrel-type Pb⋯N connections, which are further augmented by weak exchange-correlation driven C-H⋯N hydrogen bonds as well as London dispersion forces due to metallocycle units. The diffuse reflectance spectrum of [Pb3L2(N3)4]n revealed a broad band with two maxima in the UV region, corresponding to intraligand transitions, and an intense shoulder in the visible region, corresponding to metal-to-ligand charge-transfer. The latter shoulder explains the observed yellow colour of the complex. © 2023 The Royal Society of Chemistry.
AB - In this work we report a new PbII coordination polymer [Pb3L2(N3)4]n, which was obtained from Pb(N3)2 and 1-(pyridin-2-yl)ethylidenepicolinohydrazide (HL). The complex exhibits a 1D polymeric chain, constructed from the {[Pb3(N3)4]2+}n backbone, decorated with deprotonated organic L− ligands. The latter ligands are pentadentate and link two metal cations. The PbII ions were found to be in a N5O or N5O2 coordination environment, formed by covalent bonds. The azide ligands either bind four metals in a μ4-1,1,3,3 coordination mode or are coordinated to metal centers as terminal ligands. All the metal centers exhibit a hemidirected coordination geometry with a pronounced coordination gap, which allows the close approach of an additional nitrogen atom arising from an adjacent terminal azide ligand. A simplified underlying network of [Pb3L2(N3)4]n, without considering Pb⋯N tetrel bonds, exhibits the tetranodal 3,4,4,4-connected chain topology, while considering all Pb⋯N tetrel bonds, the binodal 4,5-connected chain topology was shown. The crystal packing of [Pb3L2(N3)4]n is reinforced by intermolecular π⋯π stacking interactions, formed by PbII-based five-membered chelate metallocycles and pyridine rings. In-depth bonding analysis using ETS-NOCV, IQA and NCI methods demonstrates that although the azide anions experience significant steric crowding due to repulsive azide-azide interactions, they are engaged in strong attractive, Coulomb dominated, dative-covalent Pb-N and tetrel-type Pb⋯N connections, which are further augmented by weak exchange-correlation driven C-H⋯N hydrogen bonds as well as London dispersion forces due to metallocycle units. The diffuse reflectance spectrum of [Pb3L2(N3)4]n revealed a broad band with two maxima in the UV region, corresponding to intraligand transitions, and an intense shoulder in the visible region, corresponding to metal-to-ligand charge-transfer. The latter shoulder explains the observed yellow colour of the complex. © 2023 The Royal Society of Chemistry.
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U2 - 10.1039/D3CE00596H
DO - 10.1039/D3CE00596H
M3 - Article
VL - 25
SP - 5100
EP - 5108
JO - CrystEngComm
JF - CrystEngComm
SN - 1466-8033
IS - 36
ER -
ID: 46009548