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. 2024 Oct 7;63(40):18581-18588.
doi: 10.1021/acs.inorgchem.4c02182. Epub 2024 Sep 26.

A Nanosized Porous Supramolecular Lead(II)- N'-phenyl(pyridin-2-yl)methylene- N-phenylthiosemicarbazide Aggregate, Obtained Under Electrochemical Conditions

Ghodrat Mahmoudi  1   2   3 , Isabel Garcia-Santos  4 , Elena Labisbal  4 , Alfonso Castiñeiras  4 , Vali Alizadeh  5 , Rosa M Gomila  6 , Antonio Frontera  6 , Damir A Safin  7   8
Affiliations

A Nanosized Porous Supramolecular Lead(II)- N'-phenyl(pyridin-2-yl)methylene- N-phenylthiosemicarbazide Aggregate, Obtained Under Electrochemical Conditions

Ghodrat Mahmoudi et al. Inorg Chem. .

Abstract

A novel nanosized porous supramolecular nonanuclear complex [Pb9(HL)12Cl2(ClO4)](ClO4)3·15H2O·a(solvent) (1·15H2O·a(solvent)) is reported that was synthesized by electrochemical oxidation of a Pb anode under the ambient conditions in a CH3CN:MeOH solution of N'-phenyl(pyridin-2-yl)methylene-N-phenylthiosemicarbazide (H2L), containing [N(CH3)4]ClO4 as a current carrier. The supramolecular aggregate of 1 is enforced by a myriad of Pb···S tetrel bonds (TtBs) established with the thiocarbonyl sulfur atoms of adjacent species, which have been also analyzed by DFT calculations via 2D maps of ELF, Laplacian and RDG properties. Moreover, Pb···Cl TtBs with the central Cl- anion, and Pb···O TtBs with the three oxygen atoms of the ClO4- anion, were revealed. Notably, the molecular structure of 1 differs significantly from that recently reported by us [Pb2(HL)2(CH3CN)(ClO4)2]·2H2O (2·2H2O), which was obtained using a conventional synthetic procedure by reacting Pb(ClO4)2 with H2L in the same CH3CN:MeOH solution, thus highlighting a crucial role of the electrochemical conditions. The optical characteristics of the complex were investigated using UV-vis spectroscopy and spectrofluorimetry in methanol. The complex was found to be emissive when excited at 304 nm, producing a broad emission band ranging from approximately 420 to 600 nm with multiple peaks. The CIE-1931 chromaticity coordinates, calculated as (0.33, 0.24), suggest that the emission lies in the white region of the chromaticity diagram. Further investigation is needed to fully characterize the origin of this emission.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis 1
Figure 1
Figure 1
(top) The IR spectra of H2L (black) and 1·15H2O·a(solvent) (red). (middle) The 1H NMR spectrum of 1·15H2O·a(solvent) in DMSO-d6. (bottom) The UV–vis (black) and luminescence (green) in MeOH, normalized Kubelka–Munk (red and solid blue), normalized (αhν)2 (dashed blue) and (αhν)1/2 (short dashed blue) spectra of 1·15H2O·a(solvent).
Figure 2
Figure 2
Different views on the molecular structure of 1 and crystal packing of 1·15H2O·a(solvent). Hydrogen atoms were omitted for clariy. Color code: C = gold, N = blue, O = red, Cl = green, Pb = magenta; Pb···S/O/Cl tetrel bonds = cyan dashed line, π···π interaction = green dashed line.
Figure 3
Figure 3
Partial view of the X-ray structure of 1 evidencing the formation of a trimeric assembly by means of Pb···S tetrel bonds.
Figure 4
Figure 4
2D plots of the Laplacian (dashed and solid lines for negative and positive values, respectively) including the gradient lines (in gray) overlapped with the 2D RDG maps (two top plots) and 2D ELF maps (two bottom plots) for 1. The bond paths are represented as brown lines and BCPs of tetrel bonds are shown as red dots. The RDG density cutoff is 0.05 a.u.
Figure 5
Figure 5
QTAIM (bond critical point = small red spheres, bond paths = orange lines) and NCI plot (RDG = 0.5, ρ cutoff = 0.04, color scale (signλ2)ρ = ± 0.03 a.u.) of a trimeric assembly of 1 showing the charge assisted TtBs. Table shows the QTAIM values (a.u.) for the BCPs labeled a–d.
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