Syntheses, characterizations, crystal structures, DFT/TD‐DFT, luminescence behaviors and cytotoxic effect of bicompartmental Zn (II)‐dicyanamide Schiff base coordination polymers: An approach to apoptosis, autophagy and necrosis type classical cell death

Abstract

Two new Zn (II)‐dicyanamide (dca) 1‐D chain coordination polymers (CPs), [Zn (LOMe)(μ1‐dca)(μ1,5‐dca)]n (1) and [Zn (LOEt)(μ1‐dca)(μ1,5‐dca)]n (2) have been successfully synthesized from bicompartmental Schiff base ligands N,N′‐Bis(3‐methoxysalicylidenimino)‐1,3‐diaminopropane (H2LOMe), N,N′‐Bis(3‐ethoxysalicylidenimino)‐1,3‐diaminoproane (H2LOEt) respectively and structurally characterized using various spectroscopic protocols like 1H NMR, IR, Raman, UV–Vis, fluorescence as well as elemental analysis, TGA, PXRD and SCXRD studies. X‐ray single crystal study revealed that both the complexes have two different geometrical arrangement of Zn metal centres with distorted square pyramidal Zn(2) and trigonal prismatic geometry Zn(1). Ab‐initio DFT (Density functional theory) has been executed at B3LYP (Becke, 3‐parameter, Lee‐Yang‐Parr) using DGDVP (Diffuse gradient double valence polarised) basis set to explain FMO (Frontier molecular orbital), TD‐DFT (Time‐dependent density functional theory) and photovoltaic efficiency in Dye Sensitized Solar Cell (DSSC). Hirshfeld surface (HS) and 2D fingerprint plot analyses are shed more light on the non‐covalent supramolecular interactions. The steady state and time‐resolved fluorescence measurements have been conducted in DMSO and solid‐state. CPs exhibited bi‐exponential decay in DMSO as well as solid‐state where fluorescence behaviors are mainly intra‐ligand (π → π*) in nature with lifetimes in the range (1.11–1.06 ns). In particular, in vitro cytotoxic activities were evaluated towards MCF7 (breast cancer) cell line, MDA‐MB‐231 (breast carcinoma) cell line and MCF10A (breast epithelial) cell line using MTT assay. CP1 had lower cytotoxic effect against MCF7 (20 μM), MDA‐MB‐231 (15 μM) cell lines in comparison with cisplatin (42.2 ± 8, 128.2 ± 7 μM). CP1 induced classical cell death apoptosis, autophagy and necrosis. Lower IC50 value of CP1 against MDA‐MB‐231 cell line provide new insights in the development of cancer therapeutics.

Computational study on the structural, electronic, molecular and thermochemical properties of hypothetical [Tp(CO)2Mo≡C-Ph)]2+ and [L(CO)2Mo≡C-Ph)]+ carbyne complexes

“…The species with a large energy gap are harder and the smaller ones are softer. Since the E value of complex (1) is higher than that of complex (2), complex (1) is harder than complex (2) [28].…”

Modelling the structural and reactivity landscapes of tucatinib with special reference to its wavefunction-dependent properties and screening for potential antiviral activity

“…Being a time-dependent phenomenon, the electronic transitions and consequently the electronic spectra of compounds cannot be modelled by DFT simulations, instead has to use time-dependent (TD-DFT) simulations which employs Tamm-Dancoff approximations [50,51]. We used TD-DFT simulations with CAMB3LYP functional and cc-pVDZ as a basis set using IEFPCM [52] solvation model with methanol as solvent.…”

The effect of halides and coordination mode of 4-amino-2,1,3-benzothiadiazole on the luminescence properties of its Zn complexes

“…For the TD-DFT computation of coordination polymers, many studies use finite-fragment cropped models. 37–40 We have shown that in the case of chain-like coordination polymer 4 , the use of finite models gives questionable results, even though the geometry of optimised models resembles that in the crystal. We consider emerging problems and propose an interpretation using periodic TD-DFPT calculations.…”