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Anticancer activities considering cytotoxicity, apoptosis and docking have been explored in Mn(II) and Cu(II) compounds of pyridinedicarboxylates involving enclathrated Mn(II)(H 2 O) 6 guests and unusual Cu⋯O bonding interactions. [Display omitted] Two new coordination compounds of Mn(II) and Cu(II) involving 2,6-pyridinedicarboxylate viz. [Mn 3 (2,6-PDC) 4 (H 2 O) 4 ][Mn(H 2 O) 6 ]·8H 2 O (1) and [Cu(2,6-PDC)(H 2 O)(4-CNpy)]·H 2 O (2) (2,6-PDC = 2,6-pyridinedicarboxylate, 4-CNpy = 4-cyanopyridine) have been synthesized at room temperature. Compound 1 crystallizes as a co-crystal hydrate of Mn(II); whereas compound 2 is a mononuclear compound of Cu(II). Crystal structure analysis of 1 unfolds the presence of Mn(II)(H 2 O) 6 guests within the supramolecular host cavities formed by anionic complex moieties and lattice water molecules. The lattice water molecules of the compounds 1 and 2 are involved in the formation of (H 2 O) 2 cores which are enclathrated in the supramolecular host cavities. Furthermore, the unconventional anion⋯π, antiparallel CN⋯CN, CO⋯CO, CR⋯CR (CR: chelate ring) and Cu⋯O bonding interactions observed in compound 2 play crucial role to the stability of the crystal structure. Theoretical calculations confirm that the H-bonding network in 1 and anion-π, unconventional Cu···O bonds, antiparallel CO···CO along with CR···CR interactions in 2 play crucial roles in the solid state stability of the compounds. In vitro anticancer activities of the compounds considering cell viability and apoptosis assays against Dalton's lymphoma (DL) cancer cell lines reveal that the compounds induce considerable cytotoxicity in DL cells with negligible cytotoxicity in normal PBMC cells. Lactate dehydrogenase (LDH) leakage assay also unfolds the release of LDH from DL cells to extracellular space suggesting the irreversible cell death with cell membrane damage. The molecular docking simulations of the compounds further demonstrate the structure activity relationships involving the active sites of some important antiapoptotic proteins. [ABSTRACT FROM AUTHOR]

Squaraines are 1,3-disubstituted squaric acid derivatives featuring intense fluorescence in the visible. Unlike their parent compounds, N-squaraines obtained by condensation reaction between squaric acid and primary anilines are non-fluorescent compounds. The incorporation of electron-withdrawing substituents in the para position of the phenyl rings turns these compounds acidic enough to form the corresponding dianions by acid-base reaction with alkaline hydroxide in mixed DMSO-H 2 O solvent mixtures. This work reports the microwave-assisted synthesis of N-squaraines and the investigation of the optical characteristics of their dianions. The dianionic squaraines have a C 4 N 2 O 2 2− squaryl core with absorption maxima at 450–748 nm (molar absorptions up to 7.6 × 104 M−1 cm−1). The N-squaraine dianions are highly fluorescent in the 507–644 nm range (quantum yields 0.18–0.72). Due to their negative charge, and contrary to the expectations, anionic N-squaraines are chemically stable for hours in 50% v/v H 2 O–DMSO solvent mixtures. DFT calculations show the absorption bands are S 0 → S 1 excitations (HOMO → LUMO) and S 1 → S 0 transitions (LUMO → HOMO) for the emission. In both cases, the calculated wavelengths compare well with the experimental observations. [Display omitted] • Discovering the fluorescent behaviour of classical N-squaraines dianions derived from primary anilines. • Aryl rings having electron-withdrawing substituents turn N-squaraines slightly acidic. • N-squaraine dianions can be brightly fluorescent in alkaline dimethylsulfoxide-water solutions. • Experimental and calculated absorption and emission data support a simple HOMO-LUMO excitation-emission pathway. [ABSTRACT FROM AUTHOR]

In vitro antiproliferative activities have been explored in coordination polymers of Mn(II) and Zn(II) involving energetically significant structure-guiding H-bonded synthons with cyclic tetrameric {(3-Ampy)2(H 2 O)2} and {(H 2 O)4 assemblies. [Display omitted] Two new coordination polymers of Mn(II) and Zn(II) viz. {[Mn(µ-tp)(3-Ampy) 2 (H 2 O) 2 ]2(3-Ampy)·2(H 2 O)} n (1) and {[Zn(µ-succ)(3-Ampy) 2 ]·2H 2 O} n (2) (tp = terephthalate, 3-Ampy = 3-aminopyridine, succ = succinate) have been synthesized and characterized using elemental and spectroscopic analyses, TGA and single crystal X-ray diffraction techniques. Uncoordinated 3-AMpy and water molecules of the polymeric co-crystal hydrate 1 are involved in the formation of cyclic tetrameric {(3-Ampy)2(H 2 O)2} assembly which provide rigidity to the structure. The presence of guest 3-Ampy and water molecules in the voids of supramolecular Mn(II) host tetramer in 1 provides additional reinforcement to the crystal structure. The lattice water molecules of 2 are aggregated via non-covalent interactions to form discrete cyclic {(H 2 O)4} tetrameric clusters in the crystal structure. Density functional theory (DFT), non-covalent index (NCI) plot and quantum theory of atoms in molecules (QTAIM) computational analyses reveal that the supramolecular H-bonded cyclic tetrameric structure-guiding synthon in 1 and the (H 2 O) 4 cyclic water clusters in 2 have significant energetic contribution towards the stability of the polymers. In vitro anticancer activities of the compounds considering trypan blue and apoptosis assays revealed that the compounds induce concentration dependent cytotoxicity in Dalton's lymphoma (DL) cancer cells with nominal effects in normal peripheral blood mononuclear cells (PBMC) cells. Comparative analysis reveals that compound 2 induced higher apoptosis in DL cells; which is well consistent with the trypan blue exclusion assay. Molecular docking and pharmacophore modelling studies of the compounds reveal that the compound 2 significantly interacts with the antiapoptotic proteins to establish structure activity relationship (SAR). [ABSTRACT FROM AUTHOR]

[Display omitted] A new zinc (II) complex (ZnCl 2 L.) of 4- N , N -dimethylaminophenyl substituted 2,6-dipyrazinylpyridine (dppy) ligand L is reported for selective sensing of pyrophosphate anion (P 2 O 7 4-, PPi) in aqueous acetonitrile (1:1 v / v) solution (buffered with 10 mM HEPES). The colorimetric study and UV-Visible spectroscopy study showed that the zinc (II) complex selectively detects PPi over other anions. DFT calculations indicate that high exergonic reaction process as well as formation of a six-membered chelate ring between the Zn-dppy hybrid receptor and PPi enable the receptor to sense PPi with high selectivity. A new zinc(II) complex (ZnCl 2 L) of 4- N , N -dimethylaminophenyl substituted 2,6-dipyrazinylpyridine (dppy) ligand L was synthesized and used as a probe for selective sensing of pyrophosphate anion (P 2 O 7 4-, PPi) in the presence of other anions in aqueous acetonitrile (1:1 v / v) solution (buffered with 10 mM HEPES). The sensing study was visualized through colorimetric method and measurements were done using UV–Visible spectroscopy. Further, the results were also investigated by DFT calculations in order to provide an explanation to the selectivity of the Zn-dppy hybrid receptor for PPi. [ABSTRACT FROM AUTHOR]

DFT calculations have been performed to study the mixed valence nature of three linear trinuclear cobalt complexes with tetradentate N 2 O 2 donor reduced Schiff base ligands, and acetate or bezoate as anionic co-ligands. The structure directing role of several noncovalent interactions in the solid state of the complexes has been investigated. [Display omitted] Three linear mixed valence trinuclear cobalt(III)-cobalt(II)-cobalt(III) complexes, [CoII{(μ-L1)(μ-OOCCH 3)CoIII(OOCCH 3)} 2 ]⋅4H 2 O (1), [CoII{(μ-L2)(μ-OOCCH 3)CoIII(OOCCH 3)} 2 ]⋅4H 2 O (2) and [CoII{(μ-L1)(μ-OOCPh)CoIII(OOCPh)} 2 ] (3) , have been synthesized using two N 2 O 2 donor 'reduced Schiff base' ligands, H 2 L1 (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(4-chlorophenol) and H 2 L2 (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(4-bromophenol), and acetate or bezoate as anionic co-ligands. The complexes have been characterized by spectroscopic measurements and their solid state structures have been determined by single crystal X-ray diffraction analysis. DFT calculations have been performed to study the mixed valence nature of the complexes. Moreover, the structure directing role of several noncovalent interactions in the solid state of the complexes has been investigated. The interactions have been characterized by a combination of two computational tools based on the topological analysis of the electron density, which are the quantum theory of atoms-in-molecules (QTAIM) and the noncovalent interaction plot, since they are useful to reveal noncovalent interactions in the solid state. [ABSTRACT FROM AUTHOR]

Ab initio calculations were carried out on several metalloporphyrins complexed to several ligands. The experimental spectra of metalloporphyrin–ligand complexes show large upfield shifts for the ligand proton signals compared to the free ligand. These shifts are caused by the proximity of the porphyrin π-system. The 1H NMR chemical shifts of these complexes were computed via ab initio calculations using the GIAO method at several levels of theory and the obtained values agree satisfactorily with experimental results. [Copyright &y& Elsevier]

The unified bioaccessibility method (UBM) was harnessed to assess in vitro oral bioaccessibility pools of dialkyl phthalate congeners (with methyl, –ethyl, –butylbenzyl, – n -butyl, –2-ethylhexyl, and – n -octyl moieties) and bisphenol A at the 17 μg g−1 level in beach sand contaminated with polyethylene microplastics. A variety of sample preparation approaches prior to the analysis of the UBM gastrointestinal extracts, including traditional methods (protein precipitation, liquid-liquid extraction, and solid-phase extraction) and dispersive liquid-liquid microextraction (DLLME) were comprehensively evaluated for clean-up and analyte enrichment. DLLME was chosen among all tested approaches on account of the high extraction efficiency (73–95%, excluding bis(2-ethylhexyl)phthalate and di- n -octyl phthalate), high sample throughput (∼7 min per set of samples), and environmental friendliness as demonstrated by the analytical eco-scale score of 83, and the green analytical procedure index pictogram with green/yellow labeling. The release of the less hydrophobic plastic-laden compounds (dimethyl phthalate, diethyl phthalate and bisphenol A) from the contaminated sample into the body fluids was significant, with bioaccessibility values ranging from 30 to 70%, and from 43 to 74% in gastric and gastrointestinal fluids, respectively, and with relative standard deviation < 17% in all cases. The majority of the compounds were leached during gastric digestion, likely as the combined action of the low pH and the gastric enzymes. The risk exposure analysis revealed that accumulation/concentration in the body fluids is potentially relevant for dimethyl phthalate, diethyl phthalate and bisphenol A, with relative accumulation ratios ranging from 1.1 ± 0.1 to 2.6 ± 0.4. The average daily intake values for the suite of compounds, corrected with the bioaccessibility fraction, ranged from 60 to 430 ng kg of body weight−1·day−1, in all cases, far below the tolerable daily intakes, thus indicating the lack of children health risk by ingestion of microplastic-laden sand with elevated concentrations of plasticizers. Image 1 • Unified Bioaccessibility Method for plastic additives in microplastic-laden beach sand. • Evaluation of sample treatments for reliable analysis of gastric/gastrointestinal extracts. • Comparison based on extraction efficiency, precision, speed, and eco-friendliness. • Dispersive liquid-liquid microextraction as expedient approach with green credentials. • Significant bioaccessibility for dimethyl-, and diethylphthalate and bisphenol A. Oral bioaccessibility is significant for dimethyl phthalate, diethyl phthalate and bisphenol A from microplastic contaminated beach sand. [ABSTRACT FROM AUTHOR]

[Display omitted] This manuscript reports the synthesis, spectroscopic and X-ray characterization of three new vanadium(V) complexes, namely [VO 2 L1] (1) , (μ-O) 2 [V(O)(L2) 2 ]·2CH 3 CN (2) and (μ-O) 2 [V(O)(L3) 2 ]·CH 3 CN (3) [ HL1 (2-ethoxy-6-((quinolin-8-ylimino)methyl)phenol), HL2 (2-(1-(2-(methylamino)ethylimino)propyl)phenol) and HL3 (2-(1-(2-(ethylamino)ethylimino)propyl)phenol)]. Complex 1 is a mononuclear dioxovanadium(V) system containing a five coordinated metal center, whilst complexes 2 and 3 are centrosymmetric dinuclear systems with two [(L)V = O] moieties [(L2)- for 2 and (L3)- for 3 ], which are linked together through asymmetrically bridging oxygen atoms. DFT calculations have been used to rationalize the different behavior of complex 1 , that is related to the lack of strong H-bond donors and strong ability to self-assemble via electrostatically enhanced π-stacking interactions. Moreover, the strength of π–π and CH–π interactions has been evaluated and the interactions have been characterized by several computational tools like MEP, QTAIM and NCI Plot. [ABSTRACT FROM AUTHOR]

Indium(III) diaryldithiophosphate complexes have been synthesized and characterized. Complex 1 is further studied by SC-XRD which shows the presence H-bonds, C–H ⋯ π and π ⋯ π interactions which is further analyzed by HSA and DFT calculations using NCI Plot index methods. [Display omitted] Mononuclear aryldithiophosphates of indium(III), In[ S 2 P { OAr } 2 ] 3 ; Ar = (3,5-CH 3) 2 C 6 H 3 (1), (3,4-CH 3) 2 C 6 H 3 (2), (2,5-CH 3) 2 C 6 H 3 (3) and (2,4-CH 3) 2 C 6 H 3 (4), have been synthesized and characterized by elemental analysis, NMR and FT-IR spectroscopy. Single crystal X-ray crystallography reveals that complex 1 belongs to the monoclinic crystal system with the space group P2 1 / c , wherein the indium ion is six fold coordinated with sulfur atoms of the dithiophosphate moiety resulting in a distorted octahedral geometry. Complex 1 contains intermolecular C⋯H, C–H⋯S, C–H⋯ π and π ⋯ π non-covalent interactions that help in attaining the stability of the molecule. A thorough Hirshfeld surface analysis (HSA) has also been carried out to scrutinize the intermolecular non-covalent interactions present within the molecule and the energetic features are evaluated using density functional theory (DFT) calculations. The non-covalent interaction plot (NCI Plot) index and molecular electrostatic potential (MEP) surfaces have also been used to characterize and rationalize the non covalent C–H⋯S, C–H⋯ π and π ⋯ π interactions. [ABSTRACT FROM AUTHOR]

Three dinuclear cobalt(III/II) mixed valence reduced Schiff base complexes have been synthesized and characterized. Supramolecular assemblies observed in the solid state of the three complexes involving the pseudohalide as electron donors have been analysed using DFT calculations, MEP surfaces and characterized using the NCI Plot index. [Display omitted] Three dinuclear cobalt(III/II) mixed valence reduced Schiff base complexes, [(N 3)CoIIIL(μ-O 2 CR1)CoII(N 3)] ( 1 ), [(SCN)CoIIIL(μ-O 2 CR2)CoII(NCS)] ( 2 ) and [(SCN)CoIIIL(μ-O 2 CR3)CoII(NCS)] ( 3 ) {H 2 L= (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol); R1CO 2 H = 4-methyl-3-nitrobenzoic acid; R2CO 2 H = benzoic acid; R3CO 2 H = 3-methyl-4-nitrobenzoic acid} have been synthesized and characterized by elemental analysis and spectral study. X-ray diffraction analysis was used to determine the structures of all three complexes. Spin density calculations have been used to determine the location of the paramagnetic cobalt(II) center in each of the dinuclear complexes. Moreover, several supramolecular assemblies (formed by CH⋯O, CH···SCN and S··· π and other interactions) observed in the solid state of the three complexes involving the pseudohalide as electron donors have been analysed using DFT calculations, molecular electrostatic potential (MEP) surfaces and characterized using the noncovalent interaction plot (NCI Plot) index. [ABSTRACT FROM AUTHOR]

In vitro antiproliferative activities have been explored in pyrazole-based Co(II) and Cu(II) compounds involving unusual double anion–π, C H⋯π(chelate) and C H⋯π(carbonyl) contacts. [Display omitted] Two coordination compounds of Co(II) and Cu(II) viz. [Co(2,6-PDC)(Hdmpz) 3 ]·H 2 O (1) and [Cu(2,6-PDC)(Hdmpz) 2 ] (2) (2,6-PDC = 2,6-pyridinedicarboxylate, Hdmpz = 3,5-dimethylpyrazole) have been synthesized and characterized using single crystal XRD, elemental analysis, TGA, electronic, FT-IR and 1H NMR spectroscopy. Crystal structure analysis of 1 and 2 reveals the presence of supramolecular assemblies involving various non-covalent interactions. The crystal structure of 1 is stabilized by a structure guiding hydrogen bonded synthon involving the lattice water molecules and unusual double anion–π interactions involving the carboxylate moieties of 2,6-PDC. Unconventional C H⋯π(carbonyl) and C H⋯π(chelate) contacts involving carbonyl moiety and the chelate ring of 2,6-PDC observed in the crystal structure of 2 also provide rigidity to the layered assemblies. Such unconventional C H⋯π contacts involving carbonyl moiety and chelate ring of 2,6-PDC are scarcely explored. DFT calculations in combination with QTAIM and NCI Plot analyses have been performed on supramolecular dimers of the compounds to explore the energetic features of the self-assembled dimers. The large dimerization energies of the dimers indicate the significance of these non-covalent interactions in governing solid state stabilities of the compounds. Antiproliferative evaluation of the compounds considering cell cytotoxicity and apoptosis assays revealed that the compounds induced significant concentration dependent cytotoxicity in Dalton's lymphoma (DL) cancer cells with nominal effects on normal PBMC cells. Molecular docking and pharmacophore modelling studies of the compounds have been further carried out to establish the structure activity relationship (SAR). [ABSTRACT FROM AUTHOR]

The review highlights the tetrel bonding interactions in the solid state of various lead(II) complexes synthesized from hydrazine based bis-pyridine Schiff base ligands, which may act as promising building blocks for the construction of 1D/2D/3D supramolecular assemblies. [Display omitted] Several works have been reported for lead(II) complexes where the tetrel bonding interactions are used as robust tools in supramolecular chemistry and crystal engineering. This review focuses light on the tetrel bonding interactions in the solid state structure of various lead(II) complexes with hydrazine based bis-pyridine Schiff base ligands. Synthetic and structural aspects of the complexes are also highlighted to have a good understanding of the topic. The hemidirectional nature of lead(II) center and formation of sigma holes (i.e., positive electrostatic potential along the sigma skeleton in MEP diagram) are the basic reason of such tetrel bonding interactuions. Different tetrel bonding interactions like Pb⋯O/S/N/Cl/Br/I lead to the formation of of 1D/2D/3D supramolecular assemblies. [ABSTRACT FROM AUTHOR]

Synthesis, supramolecular assemblies, in vitro antiproliferative activities and structure activity relationships of phenanthroline-based 2,6-pyridinedicarboxylato Cu(II) and Ni(II) compounds were investigated, including cell cytotoxicity, apoptosis assay, molecular docking and pharmacophore studies. [Display omitted] Two new coordination compounds of Cu(II) and Ni(II), viz. [Cu 2 (phen)(μ-2,6-PDC)(2,6-PDC)(H 2 O) 2 ]·4·.5H 2 O (1) and [Ni(phen)(2,6-PDC)(H 2 O)]·2H 2 O (2) (phen = 1,10-phenanthroline; 2,6-PDC = 2,6-pyridinedicarboxylate), have been synthesized under ambient conditions and further characterized using single crystal X-ray diffraction, FTIR, electronic spectroscopy, thermal and elemental analysis. The compound 1 is a 2,6-PDC bridged dinuclear Cu(II) compound, whereas compound 2 crystallizes as a mononuclear Ni(II) compound. Crystal structure analysis and DFT calculations reveal that the non-covalent cooperative π-stacking interactions involved in the supramolecular association of the compounds are energetically significant. In vitro antiproliferative activities of the compounds have been investigated with the Dalton's Lymphoma (DL) malignant cancer cell line using MTT cell viability and apoptosis assays. Both the compounds exhibit significant concentration dependent cell cytotoxicity and apoptotic cell death in DL cancer cells, with nominal effects for normal healthy PBMC cells. A decrease in the MMP (mitochondrial membrane potential) and a rapid increase of the ROS (reactive oxygen species) levels in DL cells corroborate the apoptotic cell death induced by the compounds. To support the observed wet lab cytotoxicity in DL cancer cells, we have also carried out in silico molecular docking studies of the compounds with the active sites of antiapoptotic BCL family proteins. Both the Cu(II) and Ni(II) compounds exhibit significant interaction modes with the BCL family cancer target proteins. Pharmacophore features of the structures of the compounds have been identified to establish a structure activity relationship (SAR). [ABSTRACT FROM AUTHOR]

Unconventional supramolecular assemblies involving inclusion of complex cationic moieties within the supramolecular host cavities of metal–organic multi-component compounds of Mn(II) and Zn(II). [Display omitted] In the present study, we have reported the synthesis of two new dinuclear Mn(II) and Zn(II) metal–organic compounds, [Mn(2,5-PDC)(phen) 2 ][Mn(phen) 2 (H 2 O) 2 ]2Cl·10H 2 O (1) and [Zn(phen) 3 ][Zn(2,6-PDC) 2 ]·11.5H 2 O (2) (where, 2,5-PDC = 2,5-pyridinedicarboxylate, 2,6-PDC = 2,6-pyridinedicarboxylate, phen = 1,10-phenanthroline) at room temperature which have been characterized by elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction techniques. A fascinating chloride-water supramolecular cluster in 1 and (H 2 O) 13 H-bonded cluster in 2 along with π-stacked assemblies stabilize the solid state structures. The most interesting aspect of the crystal structure of 1 is the inclusion of complex cationic moieties within the infinite self-assembled chloride-water cluster. Similarly the inclusion of cationic complex moieties in compound 2 inside the supramolecular cavity formed by the anionic complex provides rigidity to the crystal structure. DFT calculations, molecular electrostatic potential (MEP) surface analysis, quantum theory of atoms-in-molecules (QTAIM) and the non-covalent index plot (NCI plot) analysis were performed to investigate the supramolecular assemblies of the compounds. The studies reveal that the antiparallel π-stacking interactions are energetically significant synthons for the assemblies. However, the assemblies in 2 have been dominated mostly by Columbic attraction of the cationic and anionic complex moieties. [ABSTRACT FROM AUTHOR]

[Display omitted] Two Mn(II) and Ni(II) coordination complexes viz. [Mn(phen) 2 (2,6-PDC)]·2CH 3 OH (1) and [Ni(2,6-PDC) 2 ][Ni(H 2 O) 4 (en)]·6H 2 O (2) (phen = 1,10-phenanthroline, 2,6-PDC = 2,6-pyridinedicarboxylate and en = ethylenediamine) have been isolated at ambient conditions and characterized by elemental analysis, FT-IR, electronic spectroscopy, TGA and single crystal X-ray diffraction. Switching the solvent from methanol to water has changed the structural topologies of the compounds. Compound 1 is composed of a hepta-coordinated Mn(II) centre with two bidentate phen and one tridentate 2,6-PDC ; whereas compound 2 is composed of cationic [Ni(H 2 O) 4 (en)]2+ and anionic [Ni(2,6-PDC) 2 ]2– moieties with hexa -coordinated Ni(II) centers. Crystal structure analysis of compound 1 unfolds the presence of unorthodox O H(methanol)⋯π interactions involving the uncoordinated methanol molecules. The unusual enclathration of dual H-bonded guest (H 2 O) 4 cores in the hexameric Ni(II) hosts in compound 2 provides rigidity to the crystal structure. The antiparallel π-stacked dimers and anti-cooperative HB···anion-π···HB assemblies observed in the solid-state structures of 1 and 2 respectively have been studied theoretically using DFT calculations and NCI plot index computational tools. In vitro anticancer evaluation of the compounds considering cell cytotoxicity and apoptosis assay showed significant concentration dependent cytotoxicity in Dalton's lymphoma (DL) cancer cells with nominal effects in normal PBMC cells. To elucidate the possible mode of action of the cytotoxic behavior of the compounds, in silico docking studies have been carried out which revealed the efficient interaction of the compounds with the active sites of antiapototic cancer target proteins. The inhibitions of the activities of antiapoptotic target proteins have been further investigated using western blot analysis. [ABSTRACT FROM AUTHOR]

In vitro antiproliferative activities of benzoato bridged dinucler Mn(II) and Cu(II) compounds involving enclathrated guest chlorobenzoates and dimeric paddle wheel supramolecular assemblies. [Display omitted] Two new benzoato bridged Mn(II) and Cu(II) dinuclear coordination compounds viz. [Mn 2 (bipy) 2 (4-Clbz) 2 (H 2 O) 4 ]2(4-Clbz) (1) and [Cu 2 (bz) 4 (2-MePy) 2 ] (2) (bipy = 2,2́-bipyridine, 4-Clbz = 4-chlorobenzoate, bz = benzoate, 2-MePy = 2-methylpyridine) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic, EPR) and single crystal X-ray diffraction techniques. Crystal structure analysis of compound 1 reveals the enclathration of guest 4-Clbz moiety in the supramolecular host tetramer which provides rigidity to the crystal structure. Further analysis reveals the presence of cooperative (π–π) 2 /(π–π) 1 /(π–π) 2 ternary assemblies involving alternate coordinated and uncoordinated 4-Clbz moieties. In compound 2 , intermolecular C H∙∙∙O, C H∙∙∙π and C H∙∙∙C contacts are involved in the formation of dimeric paddle wheel supramolecular assemblies which stabilizes the layered architecture. The cooperative interplay of H-bonding and π-stacked ternary assemblies of 1 has been studied theoretically using DFT calculations, MEP surface and NCI Plot computational tools. The large interaction energies along with the NCI plot index analysis confirm that the π-stacking assemblies in combination with the H-bonds are strong binding motifs. In vitro anticancer activity of the compounds considering cytotoxicity and apoptosis assays reveal significant concentration dependent cytotoxicity in Dalton's lymphoma (DL) cancer cell lines with nominal effects in normal healthy PBMC cells. Molecular docking study reveals the efficient interaction of the compounds with the antiapoptotic BCL family target proteins. [ABSTRACT FROM AUTHOR]

Noncovalent supramolecular assemblies in two dinuclear zinc(II) complexes with different Schiff base ligands have been studied experimentally and theoretically. [Display omitted] Two new dinuclear zinc(II) complexes, [(DMSO)Zn(L1)Zn(NCS) 2 ] (1) and [ClZn(L2)ZnCl(H 2 O)]∙2CH 3 OH (2), using two different Schiff base ligands, {H 2 L1 = 2,2′-[(2,2-Dimethyl-1,3-propanediyl)bis(nitrilomethylidyne)]bis[4-bromo-6-methoxyphenol] and H 2 L2 = 2,2′-[(2,2-Dimethyl-1,3-propanediyl)bis(nitrilomethylidyne)]bis[6-ethoxyphenol]}, have been synthesized and characterized by different spectroscopic techniques. The structure guiding non-covalent interactions observed in the solid-state structure of both complexes have been analyzed using DFT calculations, MEP surface analysis, and QTAIM/NCIplot computational tools. The differences in the crystal packing and non-covalent interactions have also been studied using hirshfeld surface analyses and energy frameworks. [ABSTRACT FROM AUTHOR]

Theoretical calculations have been used to analyze and characterize the conventional π···π stacking and CH···π(arene) interactions and unconventional CH···π(pseudohalide) interactions in a cyclic tetranuclear cobalt(III)/sodium complex and a bent trinuclear CoIII(S=0)-CoII(S=3/2)-CoIII(S=0) complex. [Display omitted] A cyclic tetranuclear cobalt(III)/sodium complex, [{(N 3)CoIII(L1)Na(DMSO)}(μ 1,3 -N 3) 2 {(N 3)CoIII(L1)Na(OH 2)}] 2 ⋅0.5CH 3 OH (1) and a bent trinuclear mixed valence complex [CoII{(μ-L2)(μ-OAc)CoIII(NCS)} 2 ]⋅CH 3 CN⋅0.5H 2 O (2) have been prepared and their molecular structures have been determined by X-ray crystallography [H 2 L1 = N,N'-bis(3-methoxysalicylidene)-2,2-dimethyl-1,3-diaminoproane, H 2 L2 = N,N'-bis(2-hydroxynaphthylmethylidene)propane-1,3-diamine]. Complex 1 contains two cobalt(III) and two sodium centers, while on the other hand, complex 2 contains a high-spin Co(II) and two terminal low-spin Co(III) centers in a CoIII(S = 0)-CoII(S = 3/2)-CoIII(S = 0) trimer, as confirmed by DFT calculations Theoretical calculations have been used to analyze the importance of CH···π interactions involving the π-systems of the pseudohalide ligands. Indeed apart from the formation of conventional π···π stacking and CH···π(arene) interactions both complexes exhibit CH···π(pseudohalide) interactions that have been evaluated energetically by using mutated dimers and characterized by means of QTAIM and NCI plot computational methods which can be used to clarify interactions in real space. [ABSTRACT FROM AUTHOR]