Reconciling Local Coupled Cluster with Multireference Approaches for Transition Metal Spin-State Energetics.

Spin-state energetics of transition metal complexes remain one of the most challenging targets for electronic structure methods. Among single-reference wave function approaches, local correlation approximations to coupled cluster theory, most notably the domain-based local pair natural orbital (DLPNO) approach, hold the promise of bringing the accuracy of coupled cluster theory with single, double, and perturbative triple excitations, CCSD(T), to molecular systems of realistic size with acceptable computational cost. However, recent studies on spin-state energetics of iron-containing systems raised doubts about the ability of the DLPNO approach to adequately and systematically approximate energetics obtained by the reference-quality complete active space second-order perturbation theory with coupled-cluster semicore correlation, CASPT2/CC. Here, we revisit this problem using a diverse set of iron complexes and examine several aspects of the application of the DLPNO approach. We show that DLPNO-CCSD(T) can accurately reproduce both CASPT2/CC and canonical CCSD(T) results if two basic principles are followed. These include the consistent use of the improved iterative (T1) versus the semicanonical perturbative triple corrections and, most importantly, a simple two-point extrapolation to the PNO space limit. The latter practically eliminates errors arising from the default truncation of electron-pair correlation spaces and should be viewed as standard practice in applications of the method to transition metal spin-state energetics. Our results show that reference-quality results can be readily achieved with DLPNO-CCSD(T) if these principles are followed. This is important also in view of the applicability of the method to larger single-reference systems and multinuclear clusters, whose treatment of dynamic correlation would be challenging for multireference-based approaches.

Antifungal and antiaflatoxigenic assessment of new Cu(II)-pq complexes against Aspergillus parasiticus, in dark conditions and under visible irradiation.

The issue of food contamination by fungi and aflatoxins; constitutes a serious concern not only for human/animal health but also for agriculture and the economy. Aflatoxins are secondary metabolites produced by certain filamentous fungi and contaminate a variety of foodstuffs. In this context, control of fungal growth and aflatoxin contamination appears to be important. The present study aimed to investigate new Cu(I) and Cu(II)-quinoxaline complexes, namely [Cu(2,2´-pq)(NO3)](NO3) (1), [Cu(2,2´-pq)2(NO3)](NO3)·6H2O (2) and [Cu(2,2΄-pq)2](BF4) (3), where 2,2´-pq is 2-(2'-pyridyl quinoxaline), as antifungal agents against Aspergillus parasiticus. All complexes, the ligand and the starting material Cu(NO3)2-3H2O, regardless of the concentration used, caused inhibition of A. parasiticus growth ranged from 8.52 to 33.33%. The fungal growth inhibition was triggered when irradiation in visible (λ > 400 nm) was continuously applied (range 18.36-57.20%). The highest inhibitory activity was exhibited by the complex [Cu(2,2´-pq)2(NO3)](NO3)·6H2O and for this reason, it was selected to be studied for its ability to suppress aflatoxin B1 produced by A. parasiticus. AFB1 production after the irradiation process was found to be suppressed by 25% compared to AFB1 produced in dark conditions.

Synthesis, DNA-Binding, Anticancer Evaluation, and Molecular Docking Studies of Bishomoleptic and Trisheteroleptic Ru-Diimine Complexes Bearing 2-(2-Pyridyl)-quinoxaline.

Herein, we report the synthesis and characterization of a bishomoleptic and a trisheteroleptic ruthenium (II) polypyridyl complex, namely, [Ru(bpy)2(2, 2'-pq)](PF6)2 (1) and [Ru(bpy) (phen) (2, 2'-pq)](PF6)2 (2), respectively, where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and 2, 2'-pq = 2-(2'-pyridyl)-quinoxaline. The complexes were characterized by elemental analysis, TGA, 1H-NMR, FT-IR, UV-Vis, emission spectroscopy, and electrochemistry. Their structures were confirmed by single-crystal X-ray diffraction analysis. Complexes 1 and 2 were crystalized in orthorhombic, Pbca, and monoclinic, P21/n systems, respectively. Various spectroscopic techniques were employed to investigate the interaction of both complexes with calf thymus DNA (CT-DNA). The experimental data were confirmed by molecular docking studies, employing two different DNA sequences. Both complexes, 1 and 2, bind with DNA via a minor groove mode of binding. MTT experiments revealed that both complexes induce apoptosis of MCF-7 (breast cancer) cells in low concentrations. Confocal microscopy indicated that 2 localizes in the nucleus and internalizes more efficiently in MCF-7 than in HEK-293.

Surfactant Effects on the Synthesis of Redox Bifunctional V2O5 Photocatalysts.

Novel V2O5 bifunctional photocatalysts were prepared following a wet chemical process with the addition of anionic or non-ionic surfactants into the precursor solution and further heating under reflux. Detailed characterization and investigation of the relevant light-matter interactions proved that surfactants addition had a strong impact on the morphology, while also affecting the crystallinity, the optoelectronic properties, and the surface chemistry of the novel photocatalysts. The most efficient photocatalyst (T80) was based on tween 80, a surface-active agent employed for the first time in the synthesis of vanadium oxide materials. T80 presented crystalline nature without structural defects, which are usually centers of e- - h+ recombination. This material also exhibited small crystal size, high porosity, and short migration paths for the charge carriers, enabling their effective separation during photocatalysis. Under UV light illumination, T80 was capable to reduce hexavalent chromium to trivalent up to 70% and showed high yields in degrading methylene blue azo-dye and tetracycline antibiotic water pollutants. This remarkably high bifunctional performance defines T80 as a promising and capable photocatalytic material for both advanced oxidation and reduction processes (AOPs-ARPs).

Synthesis, characterization, DNA binding and cytotoxicity studies of two novel Cu(II)-2-(2'-pyridyl) quinoxaline complexes.

Two novel copper (II) complexes, namely [Cu(2,2'-pq)(NO3)](NO3) (1) and [Cu(2,2'-pq)2(NO3)](NO3)·6H2O(2) where 2,2'-pq is 2-(2'-pyridyl quinoxaline) were synthesized and characterized by various spectral methods. Complex 2 characterized by single crystal X-ray diffraction showed a distorted trigonal bipyramidal geometry and crystallized together with an hexamer, (H2O)6 cluster, with R66(12) topology and chair conformation. The interaction of Calf Thymus DNA (CT-DNA) with 1 and 2 was investigated by UV-Visible absorption spectra, Viscosity, Cyclic Voltammetry, Fluorescence and Circular Dichroism (CD), indicating that both complexes can bind to DNA both by means of intercalation and groove binding. Their DNA interaction mode depends on their concentrations and the differences between their structures. Cleavage experiments were performed by agarose gel electrophoresis using pBR322 DNA both in dark and after illumination. Furthermore, the cytotoxicity of both complexes was evaluated against MCF-7 and healthy cells (HEK-293) by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays; moreover their cell uptake against MCF-7 tumor cells and HEK-293 normal cells was revealed by using confocal laser scanning. Both complexes have the potential to act as effective anticancer drugs with 2 to present an IC50 smaller than that of cis-platin and also to be useful for optically probing tumor cells since it fluoresces at blue and green when is treated with MCF-7 cells.

Proton reduction reaction catalyzed by homoleptic nickel bis-1,2-dithiolate complexes: Experimental and theoretical mechanistic investigations.

A series of homoleptic monoanionic nickel dithiolene complexes [Ni(bdt)2](NBu4), [Ni(tdt)2](NBu4), and [Ni(mnt)2](NBu4) containing the ligands benzene-1,2-dithiolate (bdt2-), toluene-3,4-dithiolate (tdt2-) and maleonitriledithiolate (mnt2-), respectively, have been employed as electrocatalysts in the hydrogen evolution reaction with trifluoroacetic acid as proton source in acetonitrile. All complexes were active catalysts with TONs reaching 113, 158 and 6 for [Ni(bdt)2](NBu4), [Ni(tdt)2](NBu4), and [Ni(mnt)2](NBu4), respectively. Faradaic yield for hydrogen evolution reaction reaches 88 % for 2- , which also displays the minimal overpotential requirement value (467 mV) within the series. Two pathways for H2 evolution can be hypothesized that differ on on the sequence of protonation and reduction steps. DFT calculations are in agreement with experimental data and indicate that protonation at sulfur follows reduction to the dianion. Hydrogen evolves from the direduced-diprotonated form via a highly distorted nickel hydride intermediate. The effects of acid strength and concentration in the hydrogen-evolving mechanism are also discussed.

Experimental and Theoretical Insight into Electrocatalytic Hydrogen Evolution with Nickel Bis(aryldithiolene) Complexes as Catalysts.

A series of neutral and monoanionic nickel dithiolene complexes with p-methoxyphenyl-substituted 1,2-dithiolene ligands have been prepared and characterized with physicochemical methods. Two of the complexes, the monoanion of the symmetric [Ni{S2C2(Ph-p-OCH3)2}2] (3(-)) with NBu4(+) as a counterion and the neutral asymmetric [Ni{S2C2(Ph)(Ph-p-OCH3)}2] (2), have been structurally characterized by single-crystal X-ray crystallography. All complexes have been employed as proton-reducing catalysts in N,N-dimethylformamide with trifluoroacetic acid as the proton source. The complexes are active catalysts with good faradaic yields, reaching 83% for 2 but relatively high overpotential requirements (0.91 and 1.55 V measured at the middle of the catalytic wave for two processes observed depending on the different routes of the mechanism). The similarity of the experimental data regardless of whether the neutral or anionic form of the complexes is used indicates that the neutral form acts as a precatalyst. On the basis of detailed density functional theory calculations, the proposed mechanism reveals two different main routes after protonation of the dianion of the catalyst in accordance with the experimental data, indicating the role of the concentration of the acid and the influence of the methoxy groups. Protonation at sulfur seems be more favorable than that at the metal, which is in marked contrast with the catalytic mechanism proposed for analogous cobalt dithiolene complexes.

Re(I) tricarbonyl complex of 1,10-phenanthroline-5,6-dione: DNA binding, cytotoxicity, anti-inflammatory and anti-coagulant effects towards platelet activating factor.

The complex fac-[Re(CO)3(phendione)Cl] (1) (where phendione=1,10-phenanthroline-5,6-dione) has been synthesized and fully characterized by UV-visible, FTIR, and NMR techniques. The DNA binding properties of 1 are investigated by UV-spectrophotometric (melting curves), covalent binding assay, CV (cyclic voltammetry), circular dichroism (CD) and viscosity measurements. Experimental data indicate that 1 fits into the major groove without disrupting the helical structure of the B-DNA in contrast to the free phendione which intercalates within the base pairs of DNA. Upon irradiation, complex 1 promotes the cleavage of plasmid pBR322 DNA from supercoiled form I to nicked form II via a proton coupled electron transfer mechanism. This comes as a result of experimental data in anaerobic/aerobic conditions and in the presence of DMSO. The biological activities of 1 and its precursors [Re(CO)5Cl] and phendione are tested towards a series of cancerous cell lines as glioblastoma (T98G), prostate cancer (PC3) and breast cancer (MCF-7) as well as platelet activating factor (PAF)-aggregation. Moreover, all the aforementioned compounds are tested for their ability to modulate PAF-basic metabolic enzyme activities in preparations of rabbit leukolytes. The in vitro experiments indicate that phendione has a better antitumor effect than cisplatin whereas [Re(CO)5Cl] is a better PAF inhibitor than both the phendione ligand and 1. Moreover, for the first time it is indicated that [Re(CO)5Cl], with a IC50 of 17nM is comparable to the widely used PAF receptor antagonists, BN52021 and WEB2170 with IC50 of 30 and 20nM, respectively, whereas 1 affects PAF-catabolism.

Role of the acceptor in tuning the properties of metal [M(II) = Ni, Pd, Pt] dithiolato/dithione (donor/acceptor) second-order nonlinear chromophores: combined experimental and theoretical studies.

The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N'-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1-3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P-1), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C2S2MS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M-S bond distances involving the two ligands are similar, while the C-S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1-3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1-3 as well as on [Pt(Bz2pipdt)(mnt)] (4) and [Pt(Bz2pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (δ2) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the π system of its dithiolate ligand, dmit.

Combined experimental and theoretical study on redox-active d8 metal dithione-dithiolato complexes showing molecular second-order nonlinear optical activity.

Synthesis, characterization, NLO properties, and theoretical studies of the mixed-ligand dithiolene complexes of the nickel triad [M(II)(Bz(2)pipdt)(mnt)] (Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione, mnt = maleonitriledithiolato, M(II) = Ni, 1, Pd, 2, Pt, 3) are reported. Molecular structural characterization of 1-3 points out that four sulfur atoms are in a slightly distorted square-planar geometry. While the M-S bond distances are only slightly different, comparison of the C-C and C-S bonds in the C(2)S(2)MS(2)C(2) core allows us to point out a significant difference between the C-C and the C-S distances in Bz(2)pipdt and mnt. These findings suggest assigning a dithiolato character to mnt (pull ligand) and a dithione one (push ligand) to Bz(2)pipdt. Cyclic voltammetry of 1-3 exhibits two reversible reduction waves and a broad irreversible oxidation wave. These complexes are characterized in the visible region by a peak of moderately strong intensity, which undergoes negative solvatochromism. The molecular quadratic optical nonlinearities were determined by the EFISH technique, which provided the following values µß(λ) (10(-48) esu) = -1436 (1), -1450 (2), and -1950 (3) converted in µß(0) (10(-48) esu) = -463 (1), -684 (2), and -822 (3), showing that these complexes exhibit large negative second-order polarizabilities whose values depend on the metal, being highest for the Pt compound. DFT and TD-DFT calculations on 1-3 allow us to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated, and the results obtained support that the most appealing candidate as a second-order NLO chromophore is the platinum compound. This is due to (i) the most extensive mixture of the dithione/metal/dithiolato orbitals, (ii) the influence of the electric field of the solvent on the frontier orbitals that maximizes the difference in dipole moments between the excited and the ground state, and (iii) the largest oscillator strength in the platinum case vs nickel and palladium ones.

Synthesis, Characterization, DNA Binding, and Photocleavage Activity of Oxorhenium (V) Complexes with alpha-Diimine and Quinoxaline Ligands.

The complex [ReOCl(3)pq] (1) (where pq = 2-(2'pyridyl)quinoxaline) has been synthesized and fully characterized by UV-Vis, FTIR, 1 and 2D NMR, and cyclic voltammetry (CV). The DNA-binding properties of the complex 1 as well as of the compounds [ReOCl(3)bpy] (2), [ReOCl(3)phen] (3), and pq (4) were investigated by UV-spectrophotometric (melting curves), CV (cyclic voltammetry), and viscosity measurements. Experimental data suggest that complex 1 intercalates into the DNA base pairs. Upon irradiation, complex 1 was found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form I to nicked form II. The mechanism of the DNA cleavage by complex 1 was also investigated.

Isolation, characterization, and computational studies of the novel [Mo3(mu3-Br)2(mu-Br)3Br6]2- cluster anion.

The novel trimolybdenum cluster [Mo(3)(mu(3)-Br)(2)(mu-Br)(3)Br(6)](2-) (1, {Mo(3)}(9+), 9 d-electrons) has been isolated from the reaction of [Mo(CO)(6)] with 1,2-C(2)H(4)Br(2) in refluxing PhCl. The compound has been characterized in solution by electrospray ionization mass spectrometry (ESI-MS), UV-vis spectroscopy, cyclic voltammetry, and in the solid state by X-ray analysis (counter-cations: (n-Bu)(4)N(+) (1), Et(4)N(+), Et(3)BzN(+)), electron paramagnetic resonance (EPR), magnetic susceptibility measurements, and infrared spectroscopy. The least disordered (n-Bu)(4)N(+) salt crystallizes in the monoclinic space group C2/c, a = 20.077(2) A, b = 11.8638(11) A, c = 22.521(2) A, alpha = 90 deg, beta = 109.348(4) deg, gamma = 90 deg, V = 5061.3(9) A(3), Z = 4 and contains an isosceles triangular metal arrangement, which is capped by two bromine ligands. Each edge of the triangle is bridged by bromine ions. The structure is completed by six terminal bromine ligands. According to the magnetic measurements and the EPR spectrum the trimetallic core possesses one unpaired electron. Electrochemical data show that oxidation by one electron of 1 is reversible, thus proceeding with retention of the trimetallic core, while the reduction is irreversible. The effective magnetic moment of 1 (mu(eff), 1.55 mu(B), r.t.) is lower than the spin-only value (1.73 mu(B)) for S = 1/2 systems, most likely because of high spin-orbit coupling of Mo(III) and/or magnetic coupling throughout the lattice. The ground electronic state of 1 was studied using density functional theory techniques under the broken symmetry formalism. The ground state is predicted to exhibit strong antiferromagnetic coupling between the three molybdenum atoms of the core. Moreover, our calculated data predict two broken symmetry states that differ only by 0.4 kcal/mol (121 cm(-1)). The antiferromagnetic character is delocalized over three magnetic orbitals populated by three electrons. The assignment of the infrared spectra is also provided.

Synthesis, characterization, DFT studies and DNA binding of mixed platinum (II) complexes containing quinoxaline and 1,2-dithiolate ligands.

The complexes Pt(pq)Cl2(1) and Pt(pq)(bdt) (2) (where pq = 2-(2'pyridyl)quinoxaline and bdt=benzene-1,2-dithiolate) have been synthesized and fully characterized by UV-visible (UV-Vis), Fourier Transformer Infrared Spectra (FTIR), 1 and 2D NMR and cyclic voltammetry (CV). Interactions of the tested systems (the aforementioned complexes 1 and 2) and the free ligands pq and bdt with double stranded calf thymus DNA (CT-DNA) were studied by UV-spectrophotometric (melting curves) and circular dichroism (CD) measurements. The results suggest that both complexes 1 and 2, are able to form adducts with DNA and to distort the double helix by changing the base stacking. Complex 2 forms stronger adducts to CT-DNA than complex 1 and this is probably due to the substitution of the chlorine atoms of 1 by the 1,2-dithiolate ligand (bdt) in 2. The latter induces an extensive distortion in the planarity of 2 as density functional theory (DFT) calculations reveal. Besides, the light absorbing complex 2 possess intense mixed metal ligand to ligand charge transfer (MM'LLCT) transition in the visible region of the spectrum and could act as photoluminescent metal-based probe for the study of DNA binding. Thus, the photocleavage of DNA by 2 has been studied by UV-Vis and CD spectra and monitored by agarose gel electrophoresis. Under our experimental conditions, it is unclear that complex 2 can photocleave DNA. Furthermore, the ability of 2 to inhibit proliferation of human tumor cell lines was tested and the results indicate some cytoxytic effect on the SF-286 cells.

A vibrational and DFT study of M(diimine)(dithiolate) complexes and their complexation route.

A complete vibrational spectra analysis of the Pd(phen)(bdt), the free ligands, where phen=1,10-phenanthroline and bdt=1,2-benzenedithiolate and the starting material of its synthesis, Pd(phen)Cl(2), is performed in this paper. The molecular geometry, binding and spectroscopic properties for the aforementioned compounds are studied in detail by FT-IR, Raman and DFT methods using B3LYP functional together with basis sets of valence triple-zeta quality. Further, changes in FT-IR and Raman spectra during complexation are monitored revealing the electron delocalization over ligands. They are also consistent with pi-back donation theory.

Synthesis, characterization, and crystal structure of the Pd(phen)(bdt) complex. A DFT and TDDFT study of its ground electronic and excited states compared to those of analogous complexes.

The synthesis and characterization of Pd(phen)(bdt) (1) (phen = 1,10-phenanthroline, bdt = 1,2-benzenedithiolate) is presented. 1 crystallizes in the monoclinic space group P2(1)/c, alpha = 11.281(4) A, b = 20.498(8) A, c = 8.374(3) A, beta = 90.234(8), V = 1936.5(13) A(3), Z = 4, and is isostructural with its previously reported related complexes. The ground and low lying excited electronic states in 1 and in the related complexes Pd(bpy)(bdt) (2), Pt(bpy)(bdt) (3), Pt(bpy)(mnt) (4), and Pt(bpy)(edt) (5) [where bpy = 2,2'-bipyridine, edt = ethylene-1,2-dithiolate, and mnt = maleonitriledithiolate] are studied using density functional theory techniques. The electronic properties of 1-5 are studied using the B3LYP functional. Optimized geometries are compared to experimentally observed structures. Time dependent density functional theory (TDDFT) is employed to investigate the excited singlet and triplet states. The calculated energies of the lowest singlet state and the lowest triplet state in all five complexes are in considerable agreement with experimental data. It is shown that variation of both metal and dithiolate-ligand going from 1 and 2 to 3, 4, and 5 has a substantial impact on the spectroscopic and excited-state properties, indicating at the same time the mixed metal/dithiolate character of the HOMO orbital. All the low-lying transitions are categorized as MMLL'CT transitions. The emissive state of all complexes is assigned as a triplet dithiolate/metal to diimine charge transfer with differences in the structures of the emissions resulting from differences in the pi dithiolate orbital of the mnt, bdt, and edt as well as from differences in metal.