Experimental and molecular modelling demonstration of effective DNA and protein binding as well as anticancer potential of two mononuclear Cu(II) and Co(II) complexes with isothiocyanate and azide as anionic residues.

In the present study, one mononuclear Cu(II) [CuL(SCN)] (1) and one mononuclear Co(II) [CoLN3] (2) complexes, with a Schiff base ligand (HL) formed by condensation of 2-picolylamine and salicylaldehyde, have been successfully developed and structurally characterized. The square planer geometry of both complexes is fulfilled by the coordination of one deprotonated ligand and one ancillary ligand SCN-(1) or N3-(2) to the metal centre. Binding affinities of both complexes with deoxyribonucleic acid (DNA) and human serum albumin (HSA) are investigated using several biophysical and spectroscopic techniques. High values of the macromolecule-complex binding constants and other results confirm the effectiveness of both complexes towards binding with DNA and HSA. The determined values of the thermodynamic parameters support spontaneous interactions of both complexes with HSA, while fluorescence displacement and DNA melting studies establish groove-binding interactions with DNA for both complexes 1 and 2. The molecular modelling study validates the experimental findings. Both complexes are subjected to an MTT test establishing the anticancer property of complex 1 with lower risk to normal cells, confirmed by the IC50 values of the complex for HeLa cancer cells and HEK normal cells. Finally, a nuclear staining analysis reveals that the complexes have caused apoptotic cell death.

Development of Blue Phosphorescent Pt(II) Materials Using Dibenzofuranyl Imidazole Ligands and Their Application in Organic Light-Emitting Diodes.

Organic light-emitting diodes (OLEDs) are energy-efficient; however, the coordinating ligand can affect their stability. Sky-blue phosphorescent Pt(II) compounds with a C^N chelate, fluorinated-dbi (dbi = [1-(2,4-diisopropyldibenzo [b,d]furan-3-yl)-2-phenyl-1H-imidazole]), and acetylactonate (acac) (1)/picolinate (pic) (2) ancillary ligands were synthesized. The molecular structures were characterized using various spectroscopic methods. The Pt(II) Compound Two exhibited a distorted square planar geometry, with several intra- and inter-molecular interactions involving Cπ⋯H/Cπ⋯Cπ stacking. Complex One emitted bright sky-blue light (λmax = 485 nm) with a moderate photoluminescent quantum efficiency (PLQY) of 0.37 and short decay time (6.1 µs) compared to those of 2. Theoretical calculations suggested that the electronic transition of 1 arose from ligand(C^N)-centered π-π* transitions combined with metal-to-ligand charge-transfer (MLCT), whereas that of 2 arose from MLCT and ligand(C^N)-to-ligand(pic) charge-transfer (LLCT), with minimal contribution from C^N chelate to the lowest unoccupied molecular orbital (LUMO). Multi-layered phosphorescent OLEDs using One as a dopant and a mixed host, mCBP/CNmCBPCN, were successfully fabricated. At a 10% doping concentration of 1, a current efficiency of 13.6 cdA-1 and external quantum efficiency of 8.4% at 100 cdm-2 were achieved. These results show that the ancillary ligand in phosphorescent Pt(II) complexes must be considered.

Urea Decomposition Mechanism by Dinuclear Nickel Complexes.

Urease is an enzyme containing a dinuclear nickel active center responsible for the hydrolysis of urea into carbon dioxide and ammonia. Interestingly, inorganic models of urease are unable to mimic its mechanism despite their similarities to the enzyme active site. The reason behind the discrepancy in urea decomposition mechanisms between inorganic models and urease is still unknown. To evaluate this factor, we synthesized two bis-nickel complexes, [Ni2L(OAc)] (1) and [Ni2L(Cl)(Et3N)2] (2), based on the Trost bis-Pro-Phenol ligand (L) and encompassing different ligand labilities with coordination geometries similar to the active site of jack bean urease. Both mimetic complexes produced ammonia from urea, (1) and (2), were ten- and four-fold slower than urease, respectively. The presence and importance of several reaction intermediates were evaluated both experimentally and theoretically, indicating the aquo intermediate as a key intermediate, coordinating urea in an outer-sphere manner. Both complexes produced isocyanate, revealing an activated water molecule acting as a base. In addition, the reaction with different substrates indicated the biomimetic complexes were able to hydrolyze isocyanate. Thus, our results indicate that the formation of an outer-sphere complex in the urease analogues might be the reason urease performs a different mechanism.

Red-emitting ß-diketonate Eu(III) Complexes With Substituted 1,10-phenanthroline Derivatives: Optoelectronic and Spectroscopic Analysis.

A series of europium diketonate complexes with 1-phenyl-1,3-butanedione (PBD) and 1,10-phenanthroline derivatives were synthesized and explored spectroscopically. Photophysical characteristics of synthesized complexes have been investigated experimentally as well as theoretically. Photoluminescence emission spectra of complexes do not contain any peak of ligand revealing efficient transferal of energy from ligand to Eu3+ ion. Presence of peak at 611 nm corresponding to 5D0 → 7F2 transition is responsible for red emanation of ternary europium complexes. Photophysical parameters viz., Judd-Ofelt, quantum efficiency, radiative and non radiative decay rates were also estimated theoretically from LUMPAC software. Geometry optimization of complexes was done via Avogadro software. All synthesized trivalent complexes exhibit red emission which was further sustained by the position of chromaticity coordinates in CIE triangle. These red emanating materials could be utilized in designing electroluminescent display devices.

A Biophysical Study of Ru(II) Polypyridyl Complex, Properties and its Interaction with DNA.

Mononuclear Ru(II)Polypyridyl complexes of type [Ru(A)2BPIIP] (ClO4)2.2H2O, where BPIIP = 2-(3-(4-bromophenyl)isoxazole-5-yl)-1 H-imidazo [4,5-f] [1, 10] phenanthroline and A = bpy = bipyridyl (1), phen = 1,10 Phenanthroline (2), dmb = 4, 4' -dimethyl 2, 2'- bipyridine (3) & dmp = 4,4'-dimethyl-1,10 -Ortho Phenanthroline (4), were synthesized and their antibacterial activity were examined. The synthesized complexes were characterized and their interaction with DNA was studied using Computational and Biophysical methods (Absorption, emission methods, and viscosity). Molecular modelling studies were carried out for molecular geometry and electronic properties (Frontier molecular orbital HOMO-LUMO). The electrostatic potential surface contours for the complexes were analysed to give their nucleophilic level of sensitivity. The study reveals that the Ru(II) Polypyridyl complexes bind to DNA preponderantly by intercalation. The results recommend that the phen and dmp complex have more effective binding ability than the bpy and dmb, indicating the role of the ancillary ligand in determining their specificity for DNA binding. Further molecular docking studies suggested an octahedral geometry and bind to DNA by preferential binding to Guanine. The docking study additionally sustains the binding constant data acquired with the absorption and emission techniques.The results reveal that the nature of the ancillary Ligand plays a considerable role for the intercalation of the Ru(II) polypyridyl complex to DNA, which subsequently influences the antibacterial activity. Biological studies conducted on Gram-Negative (E.coli and K.pneumonia) and Gram-Positive (S. aureus and E. faecalis) bacteria establish that complex 1 and 2 were considerably active against S. aureus and E. coli.

New Insights into Optoelectronic Features of Eu(III) Complexes with Heterocyclic Ligand for Advanced Optical Applications.

Our present technological society needs the assistance of lanthanide luminescence in almost every field to meet the global energy demands. In present research work we have synthesized five (one binary and four ternary) 5-(4-methylphenyl)-2- furoic acid based Eu(III) complexes with ancillary ligands, namely, aqua (H2O), neocuproine (neo), 2, 2'-bipyridyl (bipy), bathophenanthroline (batho) and 1, 10-phenanthroline (phen). The spectroscopic analysis and photophysical features are characterized by the use of different investigative techniques. All the findings obtained from EDAX, elemental (CHN) analysis, FT-IR, NMR, UV-visible spectroscopy declared the coordination of ligand binding sites with the europium ion. These Eu(III) complexes possess good thermal stability and excellent optoelectronic features as predicted with the help of TGA and PL analysis. Diffuse reflectance spectral studies confirm their applications in the wide band gap semiconductors. The Judd-Ofelt analysis and monoexponential behavior of lifetime reveals the existence of asymmetric and single local environment around europium ion. All the complexes show sharp red emission validated by CIE color coordinates, color purity, asymmetric ratio and CCT values. SEM analysis tells that the bulk of these complexes comprised of spherical shaped particles with uniform distribution.

Coordination and Hydroboration of Ru(II)-Borate Complexes: Dihydridoborate vs. Bis(dihydridoborate).

Treatment of [Cp*RuCl2 ]2 , 1, [(COD)IrCl]2 , 2 or [(p-cymene)RuCl2 ]2, 3 (Cp*=η5 -C5 Me5, COD= 1,5-cyclooctadiene and p-cymene=η6 -i PrC6 H4 Me) with heterocyclic borate ligands [Na[(H3 B)L], L1 and L2 (L1 : L=amt, L2 : L=mp; amt=2-amino-5-mercapto-1,3,4-thiadiazole, mp=2-mercaptopyridine) led to the formation of borate complexes having uncommon coordination. For example, complexes 1 and 2 on reaction with L1 and L2 afforded dihydridoborate species [LA M(µ-H)2 BHL] 4-6 (4: LA =Cp*, M=Ru, L=amt; 5: LA =Cp*, M=Ru, L=mp; 6: LA =COD, M=Ir, L=mp). On the other hand, treatment of 3 with L2 yielded cis- and trans-bis(dihydridoborate) species, [Ru{(µ-H)2 BH(mp)}2 ], cis-7 and trans-7. The isolation and structural characterization of fac- and mer-[Ru{(µ-H)2 BH(mp)}{(µ-H)BH(mp)2 }], 8 from the same reaction offered an insight into the behaviour of these dihydridoborate species in solution. Fascinatingly, despite having reduced natural charges on Ru centres both at cis-and trans-7, they underwent hydroboration reaction with alkynes that yielded both Markovnikov and anti-Markovnikov addition products, 10 a-d.

Understanding the ancillary ligand effect on luminescent cyclometalated Ir(III) complex as a reporter for 2-acetylaminofluorene DNA(AAF-dG) adduct.

Mutagenic agents such as aromatic amines undergo metabolic activation and produce DNA adducts at C8 position of guanine bases. N-2-acetylaminofluorene (AAF) generates different mutational outcomes when placed at G1, G2, and G3 of a NarI sequence (-G1G2CG3CC/T-). These outcomes are dictated by the conformations adopted by these adducts. Detection of such lesions is of considerable interest owing to their hazardous effects. Here, we report the synthesis of three cyclometalated [Ir(L)2dppz]+ complexes (L = 2-phenylpyridine (ppy) 1; benzo[h]quinoline (bhq) 2; 2-phenylquinoline (pq) 3; dppz = dipyrido[3,2-a:2',3'-c]phenazine) and their interaction with AAF adducted NarI DNA. Remarkably, complexes 1 and 2 displayed dominant 3LC transition characteristic of polar environment despite binding to the adducted sites. On the other hand, complex 3 binds to NarI sequences and behaves as a luminescent reporter for AAF-modified DNA. The results reported here emphasize that molecular light switching phenomenon can be stimulated by switching ancillary ligands and might act as potential probes for covalent-DNA defects.

Solid-State Near-Infrared Circularly Polarized Luminescence from Chiral YbIII -Single-Molecule Magnet.

A field-induced chiral YbIII Single-Molecule Magnet (SMM) displayed an unprecedented near-infrared circularly polarized luminescence (NIR-CPL) in the solid-state. The bridging bis(1,10-phenantro[5,6b])tetrathiafulvalene triad (L) allowed an efficient sensitization of the NIR 2 F5/2 →2 F7/2 emission while the NIR-CPL is associated to the f-f transitions of the YbIII ion bearing chiral ß-diketonate derived-camphorate ancillary ligands.

Switching the Reactivity of Palladium Diimines with "Ancillary" Ligand to Select between Olefin Polymerization, Branching Regulation, or Olefin Isomerization.

Coordinating solvents are commonly employed as ancillary ligands to stabilize late transition metal complexes and are conventionally considered to have little effect on the reaction products. Our work identifies that the presence of ancillary ligand in Pd-diimine catalyzed polymerizations of α-olefins can drastically alter reactivity. The addition of different amounts of acetonitrile allows for switching between distinct reaction modes: isomerization-polymerization with high branching (0 equiv.), regular chain-walking polymerization (1 equiv.), and alkene isomerization with no polymerization (>20 equiv.). Optimization of the isomerization reaction mode led to a general set of conditions to switch a wide variety of diimine complexes into efficient alkene isomerization catalysts, with catalyst loading as low as 0.005 mol %.

Rhenium (I) Complexes as Probes for Prokaryotic and Fungal Cells by Fluorescence Microscopy: Do Ligands Matter?

Re(I) complexes have exposed highly suitable properties for cellular imaging (especially for fluorescent microscopy) such as low cytotoxicity, good cellular uptake, and differential staining. These features can be modulated or tuned by modifying the ligands surrounding the metal core. However, most of Re(I)-based complexes have been tested for non-walled cells, such as epithelial cells. In this context, it has been proposed that Re(I) complexes are inefficient to stain walled cells (i.e., cells protected by a rigid cell wall, such as bacteria and fungi), presumably due to this physical barrier hampering cellular uptake. More recently, a series of studies have been published showing that a suitable combination of ligands is useful for obtaining Re(I)-based complexes able to stain walled cells. This review summarizes the main characteristics of different fluorophores used in bioimage, remarking the advantages of d6-based complexes, and focusing on Re(I) complexes. In addition, we explored different structural features of these complexes that allow for obtaining fluorophores especially designed for walled cells (bacteria and fungi), with especial emphasis on the ligand choice. Since many pathogens correspond to bacteria and fungi (yeasts and molds), and considering that these organisms have been increasingly used in several biotechnological applications, development of new tools for their study, such as the design of new fluorophores, is fundamental and attractive.

Study of the interaction of Co(III) polypyridyl complexes with DNA: an experimental and computational approach.

Three new cobalt(III) polypyridyl complexes, [Co(L - L)2IIP]3+ where IIP = 2-(2H-isoindol-1-yl)-2H-imidazo[4,5-f][1, 10]phenanthroline, L = 1) phen (1,10-phenanthroline), 2) bpy (2,2'bipyridyl), 3) dmb (4, 4-dimethyl 2, 2'-bipyridine) have been synthesized, characterized (UV -VIS, IR, 1HNMR and 13C NMR spectroscopy) and screened for their in vitro antibacterial activity against E.coli, Staphylococcus aureus and Bacillus subtilis. The binding of these complexes with calf-thymus DNA (CT-DNA) has been investigated by absorption and fluorescence spectroscopy, viscosity measurements. The experimental studies indicate that complexes bind to CT-DNA by means of intercalation, but with different binding affinities due to differences in the planarity of the ancillary ligand. The complexes promote photocleavage of plasmid DNA from super coiled form I to the open circular form II. The antibacterial activities suggest that the metal complexes are more active as compared to the prepared un-complexed IIP ligand. In addition, a conformational search was carried out by Molecular Dynamics Simulations, and docking revealed that complexes intercalate between base pairs of DNA. The experimental and computational approaches reveal that the length of the intercalator and the nature of ancillary ligand are highly important factors for DNA binding.

Influence of different ancillary ligand on the phosphorescent properties of platinum(II) complexes.

In past two decades, lots of bidentate Pt(II) complexes are developed as potential organic light emitting diodes due to their simple synthetic process. The relative low quantum efficiency is one of the major blocks for their applications. Two new heteroleptic Pt(II) complexes bearing an n-hexyloxy substituted phenyllepidine-based ligand and either a picolinate (pic) (1) or acetylacetonate (acac) (2) ancillary ligand are synthesized as orange-red-emitter by Wawrzinek and coauthors. The quantum efficiency of 2 is much larger than that of 1 indicating that the variation of ancillary ligand has a great effect on the performance. Inspired by it, other two new bidentate Pt(II) complexes are theoretically designed with the same primary ligand along with pyrazolone (pzl) (3) or N-substituted carbazole (NCaz) (4) ancillary ligand. The phosphorescent properties are explored by density functional theory (DFT) and time dependent DFT (TDDFT) methods with the ultimate goal to explore the influence of ancillary ligand. Moreover, the emission rule is confirmed. Finally, the quantum yield is estimated according to the radiative rate constant (kr) and nonradiative rate constant (knr). The smaller knr is the vital item to determine the high quantum yield.

Enhanced quantum yields by sterically demanding aryl-substituted ß-diketonate ancillary ligands.

Luminescent organometallic platinum(II) compounds are of interest as phosphors for organic light emitting devices. Their emissive properties can be tuned by variation of the ligands or by specific electron-withdrawing or electron-donating substituents. Different ancillary ligands can have a profound impact on the emission color and emission efficiency of these complexes. We studied the influence of sterically hindered, aryl-substituted ß-diketonates on the emission properties of C^C* cyclometalated complexes, employing the unsubstituted methyl-phenyl-imidazolium ligand. The quantum yield was significantly enhanced by changing the auxiliary ligand from acetylacetonate, where the corresponding platinum(II) complex shows only a very weak emission, to mesityl (mes) or duryl (dur) substituted acetylacetonates. The new complexes show very efficient emission with quantum yields >70% in the sky-blue spectral region (480 nm) and short decay times (<3 µs).

Synthesis, Characterization, Properties and DFT Calculations of 2-(Benzo[b]thiophen-2-yl)pyridine-based Iridium(III) Complexes with Different Ancillary Ligands.

A series of new cyclometalated btp-based iridium(III) complexes with three different ancillary ligands, Ir(btp)2(bozp) (3a), Ir(btp)2(btzp) (3b) and Ir(btp)2(izp) (3c) (btp = 2-(benzo[b]thiophen-2-yl)pyridine, bozp =2-(benzo[d]oxazol-2-yl)phenol, btzp =2-(benzo[d]thiazol-2-yl)phenol, izp = 2-(2 H-indazol-2-yl)phenol), have been synthesized and fully characterized. The crystal structure of 3b has been determined by single crystal X-ray diffraction analysis. A comparative study has been carried out for complexes 3a - 3c by UV-vis absorption spectroscopy, photoluminescence spectroscopy, cyclic voltammetry and DFT calculations. This observation illustrates that the substitution of N or S in ancillary ligand can lead to a marked bathochromic shift of absorption and emission wavelengths. The spectroscopic characterisation of these complexes has been complemented by DFT and TD-DFT calculations, supporting the assignment of (3)MLCT/(3)LC to the lowest energy excited state.