New Organotin (IV) Compounds Derived from Dehydroacetic Acid and Thiosemicarbazides: Synthesis, Rational Design, Cytotoxic Evaluation, and Molecular Docking Simulation.

Organotin complexes were prepared through a one-pot reaction with three components by reacting thiosemicarbazide or 4-methyl-3-thiosemicarbazide or 4-phenylthiosemicarbazide, dehydroacetic acid (DHA) and dibutyl, diphenyl, dicyclohexyl, and bis[(trimethylsilyl)methyl]tin(IV) oxides; all complexes were characterized by infrared (IR), ultraviolet-visible (UV-vis), mass spectrometry (MS), and nuclear magnetic resonance (NMR) spectroscopy. The 119Sn NMR revealed chemical shifts corresponding to a pentacoordinated environment in solution. The X-ray crystallography of the two complexes evidenced the formation of monomeric complexes with a pentacoordinated geometry around tin via three donor atoms from the ligand, the sulfur of the thiol, the nitrogen of the imine group, and the oxygen of the pyran ring. The geometries of the five-coordinated complexes 3a (Bu2SnL3), 3c (Ph2SnL3), and 3d (Cy2SnL3) acid were intermediate between square pyramidal and trigonal bipyramidal, and complex 1a (Bu2SnL1) adopted a bipyramidal trigonal geometry (BPT). The sulforhodamine B assay assessed the cytotoxicity of organotin(IV) complexes against the MDA-MB-231 and MCF-7 (human mammary adenocarcinoma) cell lines and one normal COS-7 (African green monkey kidney fibroblast). The IC50 values evidenced a significant antiproliferative effect on cancer cells; the complexes were more potent than the positive cisplatin control and the corresponding ligands, dehydroacetic acid thiosemicarbazone (L1), dehydroacetic acid-N(4)-methylthiosemicarbazone (L2), and dehydroacetic acid-N(4)-phenylthiosemicarbazone (L3). The IC50 values also indicated that the organotin(IV) complexes were more cytotoxic against the triple-negative breast cell line MDA-MB-231 than MCF-7, inducing significant morphological alterations. The interactions of organotin(IV) 1c (Ph2SnL1), 1d (Cy2SnL1), and 1e (((CH3)3SiCH2)2SnL1) were evaluated with ss-DNA by fluorescence; intensity changes of the fluorescence were indicative of the displacement of ethidium bromide (EB), confirming the interaction of the organotin(IV) complexes with ss-DNA; the results showed a DNA binding affinity. The thermodynamic parameters obtained through isothermal titration calorimetry showed that the interaction of 1c (Ph2SnL1), with ss-ADN, was exothermic. Molecular docking studies also demonstrated that the organotin(IV) complexes were intercalated in DNA by conventional hydrogen bonds, carbon-hydrogen bonds, and π-alkyl interactions. These complexes furthermore showed a greater affinity towards DNA than cisplatin.

Pentacoordinated Organotin(IV) Complexes as an Alternative in the Design of Highly Efficient Optoelectronic and Photovoltaic Devices: Synthesis and Photophysical Characterization.

The synthesis of four pentacoordinated organotin(IV) complexes prepared in a one-pot reaction from 2-hydroxy-1-naphthaldehyde, 2-amino-3-hydroxypyridine and organotin oxides is reported. The complexes were characterized by UV-Vis, IR, MS, 1H, 13C and 119Sn NMR techniques. The compound based on 2,2-diphenyl-6-aza-1,3-dioxa-2-stannanaphtho[1,2-h]pyrido[3,2-d]cyclononene revealed the formation of a monomeric complex with a distorted five-coordinated molecular geometry intermediate between the trigonal bipyramidal and square pyramidal. In order to find possible applications in photovoltaic devices, hybrid films of organotin(IV) complexes embedded in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with graphene were deposited. The topographic and mechanical properties were examined. The film with the complex integrated into the cyclohexyl substituent has high plastic deformation, with a maximum stress of 1.69 × 107 Pa and a Knoop hardness of 0.061. The lowest values of 1.85 eV for the onset gap and 3.53 eV for the energy gap were obtained for the heterostructure having the complex with the phenyl substituent. Bulk heterojunction devices were fabricated; these devices showed ohmic behavior at low voltages and a space-charge-limited current (SCLC) conduction mechanism at higher voltages. A value of 0.02 A was found for the maximum carried current. The SCLC mechanism suggests hole mobility values of between 2.62 × 10-2 and 3.63 cm2/V.s and concentrations of thermally excited holes between 2.96 × 1018 and 4.38 × 1018 m-3.

Design of Promising Heptacoordinated Organotin (IV) Complexes-PEDOT: PSS-Based Composite for New-Generation Optoelectronic Devices Applications.

The synthesis of four mononuclear heptacoordinated organotin (IV) complexes of mixed ligands derived from tridentated Schiff bases and pyrazinecarboxylic acid is reported. This organotin (IV) complexes were prepared by using a multicomponent reaction, the reaction proceeds in moderate to good yields (64% to 82%). The complexes were characterized by UV-vis spectroscopy, IR spectroscopy, mass spectrometry, 1H, 13C, and 119Sn nuclear magnetic resonance (NMR) and elemental analysis. The spectroscopic analysis revealed that the tin atom is seven-coordinate in solution and that the carboxyl group acts as monodentate ligand. To determine the effect of the substituent on the optoelectronic properties of the organotin (IV) complexes, thin films were deposited, and the optical bandgap was obtained. A bandgap between 1.88 and 1.98 eV for the pellets and between 1.23 and 1.40 eV for the thin films was obtained. Later, different types of optoelectronic devices with architecture "contacts up/base down" were manufactured and analyzed to compare their electrical behavior. The design was intended to generate a composite based on the synthetized heptacoordinated organotin (IV) complexes embedded on the poly(3,4-ethylenedyoxithiophene)-poly(styrene sulfonate) (PEDOT:PSS). A Schottky curve at low voltages (<1.5 mV) and a current density variation of as much as ~3 × 10-5 A/cm2 at ~1.1 mV was observed. A generated photocurrent was of approximately 10-7 A and a photoconductivity between 4 × 10-9 and 7 × 10-9 S/cm for all the manufactured structures. The structural modifications on organotin (IV) complexes were focused on the electronic nature of the substituents and their ability to contribute to the electronic delocalization via the π system. The presence of the methyl group, a modest electron donor, or the non-substitution on the aromatic ring, has a reduced effect on the electronic properties of the molecule. However, a strong effect in the electronic properties of the material can be inferred from the presence of electron-withdrawing substituents like chlorine, able to reduce the gap energies.