Cl Complexes Research Articles

Computational studies on the excited state decay rates in aggregates of two‐coordinate Cu (I) complexes: Thermally Activated Delayed Fluorescence and Aggregation Induced Emis

AbstractTwo‐coordinate Cu (I) complexes have attracted great interest recently because of the rich photophysical property in solid state, including the aggregation‐induced thermal activated delayed fluorescence. Here, we summarize our theoretical investigations on the excited state structure and decay dynamics for the two‐coordinate Cu (I) complexes in solution phase and solid state by the thermal vibration correlation function rate formalism we developed earlier coupled with time‐dependent density‐functional theory within polarizable continuum model and hybrid quantum and molecular mechanics. First, for the CAACCu (I)Cl complex, we found that the nature of the excited state undergoes a change from metal‐to‐ligand charge transfer (MLCT) in solution to hybrid halogen‐to‐ligand charge transfer and MLCT in solid state. The bending vibrations of the CCuCl and CuCN bonds are restricted in aggregates, reducing the non‐radiative decay rate to cause strong solid‐state fluorescence. Second, for CAACCu (I)Cz, we found that both intersystem crossing (ISC) and reverse intersystem crossing (rISC) are enhanced by 2–4 orders of magnitudes upon aggregation, leading to highly efficient thermally activated delayed fluorescence (TADF). The enhanced ISC and rISC rates can be attributed to the increase of the metal proportion in the frontier molecular orbitals, leading to an enhanced spin−orbit coupling between S1 and T1. The reaction barriers for ISC and rISC are much lower in solution than that in aggregate phase resulting in a decrease in energy gap and an increase in the relative reorganization energy through bending the angle ∠C − Cu − N for T1. Our theoretical studies provide a clear rationalization for the highly efficient solid‐state luminescence character of two‐coordinate Cu (I) complexes and may clarify the ongoing dispute on the understanding of the high TADF quantum efficiency.

Defect Chemistry of Halogen Dopants in ZnSe.

Halogen dopants in ZnSe have been a research focus for quantum applications utilizing excitonic emissions, wherein point defects play a critical role. To provide a full first-principles perspective on the defect chemistries of halogen-doped ZnSe, Cl- and F-doped ZnSe were explored via hybrid functional density functional theory calculations involving all possible isolated defects and defect-defect complexes. Cl and F both exhibit more complicated defect chemistries than just forming a shallow substitutional donor on the Se site. For Cl, the complex of Cl substituting for Se with a neighboring Zn vacancy was also found to be prevalent. For F, its interstitial in the Zn tetrahedron was found to be stable in addition to the complex of such interstitial with an adjacent F atom substituting for Se. The explicitly simulated emission photoluminescence lineshapes of the self-activated centers exhibited both a peak value and a broad line width consistent with the experiment.

Ultrahigh carbon monoxide capture by novel protic cuprous-functionalized dicationic ionic liquids through complexation interactions

CO removal is a very important topic in the scientific and industrial communities. However, the CO capture performance of the currently reported absorbents is still unsatisfactory from an industrial perspective. Described herein have developed a series of novel protic functionalized dicationic ionic liquids (ILs) containing abundant cuprous sites for effective absorption and separation of CO. The physical properties of the prepared ILs were characterized, and the CO solubility was systematically determined. Strikingly, the solubility of CO in the designed IL [HBDMAEE-C6][Cu2Cl3]2 reaches as high as 1.440 mol/mol at 40 °C and 2.0 bar due to the accompanying phase change, which is the highest value reported so far. The interaction mechanism between [HBDMAEE-C6][Cu2Cl3]2 and CO was further elucidated by IR and NMR spectroscopy paired with Gaussian calculation, and the formation of Cu(CO)Cl complexes was confirmed. After ten consecutive absorption–desorption cycles, the CO uptake did not decrease significantly. As far as we know, this series of ILs show excellent CO capture performance and reversible regeneration performance. The strategy of multi-copper sites in this work provides important guidance for the design of novel solvents with promising applications in CO selective separation and storage.

The formation of a heterogeneous-homogeneous catalytic system for the benzene alkylation with ethylene upon interaction of aluminum and carbon tetrachloride alloys

The in situ formation of the catalytic heterogeneous-homogeneous system including the Al-M (M = Ni, Co, Cu) alloy and the Al(M)/Cl complex in a benzene-ethylene medium at a temperature of 80 °C and pressure 0.2–0.3 MPa was studied. Regularities were found in the interaction of Al-M alloys activated by the liquid-metal Ga-In eutectic with a chlorinating agent (CCl4), which led to the formation of catalytically active Al(M)/Cl metal-aluminum chloride complexes. Spectrokinetic measurements showed that reactivity of the activated alloys toward an excess of CCl4 can form the following series: Al-Cu ≈ Al-Ni > Al > Al-Co. The highest catalytic activity was observed for the nickel-aluminum chloride complexes; their selectivity to ethyl benzene was up to 48 %. According to IR and UV-vis spectroscopy data, the structure and composition of the metal-chloride complexes formed in situ in the aromatic reaction medium are determined by a combination of the coupled ion pairs [AlCl4]–tetrahed./[NiCl6]4–octahed. and [AlCl4]–tetrahed./[CuCl2]–lin. stabilized by the (C6H5)3C+ carbocation.

A New Paradigm in Pincer Iridium Chemistry: PCN Complexes for (De)Hydrogenation Catalysis and Beyond.

The discovery and development of organometallic catalysts is of paramount importance in modern organic synthesis, among which the ligand scaffolds play a crucial role in controlling the activity and selectivity. Over the past several decades, d8 transition-metal complexes of pincer ligands have been developed extensively thanks to their easy structural modification, versatile reactivities, and high stability. One paradigm is the bis(phosphine)-based pincer iridium complexes PCP-Ir, which are highly active for alkane dehydrogenation, partly due to their high thermostability. However, except for alkane dehydrogenation and related transformations, few applications of pincer iridium catalysis have been seen in organic synthesis. This mainly arises from the low functional-group compatibility and poor substrate scope and the limited catalytic chemistry that invariably involves Ir(I/III) redox processes initiated by oxidative addition of substrates to 14-electron (PCP)Ir fragments (the proposed catalytically active intermediates). In this Account, we describe our endeavor on the development of a new family of PCN-Ir complexes with initial intention on creating more efficient alkane dehydrogenation catalysts. The replacement of a soft, σ-donor phosphine arm in the PCP ligands by a harder, π-acceptor N-heteroarene (pyridine or oxazoline) not only provides an additional platform to modify the structural properties but also offers new modes of bond activation and novel reactivities and catalysis. One uniqueness of the PCN-Ir system lies in the formation, via ortho-C(sp2)-H cyclometalation of the pyridine unit in the PCNPy ligand, of the neutral monohydride (PCC)IrIIIHL (L = neutral ligand), which catalyzes positional and stereoselective 1-alkene-to-(E)-2-alkene isomerization. Moreover, the PCN-Ir catalysts effect ethanol dehydrogenation without decarbonylation, allowing for transfer hydrogenation of unactivated alkenes and trans-selective semihydrogenation of internal alkynes with user-friendly ethanol as the H-donor. Another feature originates from the ability of the pentacoordinate hydrido chloride complex (PCN)IrIIIHCl to undergo reversible solvent-coordination-induced-ionization (SCII), furnishing a cationic monohydride [(PCN)IrIIIH(Sol)]+Cl- bearing an uncoordinated Cl anion that effects selective hydrometalation of internal alkynes over the corresponding (Z)-alkenes; the resulting (PCN)IrIII(vinyl)Cl complex undergoes amine-assisted formal alcoholysis involving the protonation of the Cl anion by the activated IrIII-bound EtOH, again via the SCII pathway. Together these elementary reactions lay the foundation for cis-selective semihydrogenation of alkynes with EtOH. Further, the design of the oxazoline-containing chiral complexes (PCNOxa)IrIIIHCl enables asymmetric transfer hydrogenation of alkenes/ketones with ethanol. The efficient catalytic α-alkylation of unactivated esters/amides with alcohols is another case showing the benefit that the PCN-Ir catalyst can offer. These examples illustrate the profound impact of the pincer ligands on the reactivities and catalysis. We hope this Account will provide an in-depth view into the fundamentals of pincer iridium chemistry and ultimately broaden its applications in organic synthesis.

One-pot multi-step synthesis of high-aspect-ratio Cu nanowires based on an environment-friendly manner for low-cost and high-performance transparent conductive films

High-aspect-ratio Cu nanowires (NWs) were synthesized based on an environment-friendly synthesis method in which aqueous Cu–Cl complexes were reduced to Cu atoms in a weak ascorbic acid solution. Constant reaction temperatures led to many reduced Cu atoms relative to NWs and then the synthesized Cu atoms were deposited on the end and side faces of Cu NWs, resulting in low aspect ratios. Two-step temperature synthesis was suggested to suppress Cu atoms during the Cu NW growth. High temperatures during the early reaction stage maximized NW seeds and low temperatures in the late stage decreased the number of Cu atoms under precisely controlled temperature and temperature drop time, leading to Cu deposition on the end faces rather than side faces. Additionally, optimum Cu-source additions continuously facilitated the preferential growth in length of Cu NWs. The one-pot multi-step synthesis controlled the reduction rate of Cu complexes and substantially increased the aspect ratio of Cu NW from 313 to 760, showing that the precise control was suitable for changing the NW sizes. Finally, transparent conductive films comprising the NWs showed high performances (transmittance = 90.8 %, sheet resistance = 94 Ω/sq).

Theoretical investigation and antineoplastic potential of Zn (II) and Pd (II) complexes of 6-methylpyridine-2-carbaldehyde-N (4)-ethylthiosemicarbazone

Density Functional Theoretical (DFT) and molecular docking studies have been used to elucidate the antineoplastic potential of the ligand 6-Methylpyridine-2-carbaldehyde-N (4)-ethylthiosemicarbazone (MET) and its platinum(II) and zinc(II) complexes. The frontier molecular orbital and the global quantum reactivity parameters were used to study the reactivity and stability of the modeled complexes. The energy gap showed that the complexes have their reactivity in the order Pd[MET] < [MET] < Zn[MET] suggesting a higher reactivity of the Pd complex compared to its Zn(II) congener. NBO indicated Pd(MET)Cl complex to have the highest E(2) energies and exhibiting highest interaction arising from strong coordination of the thiolato sulfur and chloride atoms around the Pd2+ as seen in the σ*S21 -Pd13→ σ*Pd31 – Cl32 transition. QTAIM revealed that highest density of electrons follows the order [Pd(MET)Cl] >[Zn(MET)Cl] > [MET], while computational drug design protocols carried out provided the order of binding affinity as Pd(MET)Cl > Zn(MET)Cl and MET which again presents Pd complex as having greater antineoplastic activity. Our DFT findings are in excellent agreement with previous experimental reports thereby affirming the potential of these complexes as possible candidates for antineoplastic chemotherapeutic treatment against the human colon tumor cell lines (HCT 116) .

Enhanced anticancer potency with reduced nephrotoxicity of newly synthesized platin-based complexes compared with cisplatin

As a platinum-containing anticancer drug, cisplatin is the keystone for treating many malignancies. Nephrotoxicity is the main dose-limiting toxicity, and several hydration therapies and supplementary strategies are utilized to reduce cisplatin-induced kidney damage, so the discovery and development of effective and safe antitumor drugs are still on the path of human health. Herein, a new four-coordinated Pt complex [Pt(TSC)Cl] using N(4)-phenyl-2-formylpyridine thiosemicarbazone (HTSC) was synthesized and characterized by single-crystal X-ray diffraction, 1HNMR, FT-IR, LC/MS and CHN elemental analysis. The Pt(TSC)Cl complex revealed antiproliferative activity against A549, MCF-7 and Caco-2 cell lines with a low micromolar IC50 (200–1.75 µM). Specifically, the Pt(TSC)Cl complex displayed more selectivity in Caco-2 cells (IC50 = 2.3 µM) than cisplatin (IC50 = 107 µM) after 48 h of treatment. Moreover, compared with cisplatin, a known nephrotoxic drug, the Pt(TSC)Cl complex exhibited lower nephrotoxicity against Hek293 normal cells. We also found that the Pt(TSC)Cl complex can effectively prevent cancer cell propagation in sub-G1 and S phases and induce apoptosis (more than 90%). Real time PCR and western analysis demonstrated that the expression pattern of apoptotic genes and proteins is according to the intrinsic apoptosis pathway through the Bax/Bcl-2-Casp9-Casp3/Casp7 axis. Collectively, our findings indicated that the Pt(TSC)Cl complex triggers apoptosis in Caco-2 cell lines, while low nephrotoxicity was shown and may be considered a useful anticancer drug candidate for colorectal cancers for further optimization and growth.

Mesoionische Imine (MIIs): Starke Donoren und vielseitige Liganden für Übergangsmetalle und Hauptgruppensubstrate

AbstractWir berichten über die Synthese und die Reaktivität mesoionischer Imine (MIIs) des 1,2,3‐Triazolin‐5‐imin Typs. Die MIIs sind über eine Basen‐mediierte Cycloaddition eines substituierten Acetonitrils mit einem aromatischen Azid, Methylierung nach etablierten Methylierungsrouten und anschließender Deprotonierung zugänglich. C=O‐Streckschwingungen in MII−CO2− und −Rh(CO)2Cl‐Komplexen wurden bemüht um die Gesamtdonorstärke zu bestimmen. Die MIIs sind stärkere Donoren als N‐Heterocyclische Imine (NHIs). MIIs sind exzellente Liganden für Hauptgruppenelemente und Übergangsmetalle, in welchen sie Substituenten‐induzierte Fluor‐spezifische Wechselwirkungen zeigen oder C−H‐Aktvierungen eingehen. DFT‐Berechnungen haben Einblicke in die Grenzorbitale der MIIs gegeben. Die Rechnungen sagen im Vergleich zu verwandten Liganden eine relative kleine HOMO–LUMO Lücke vorraus. MIIs können potentiell sowohl als π‐Donor‐ als auch π‐Akzeptorliganden wirken. Dieser Bericht demonstiert das Potential von MIIs spannende Eigenschaften mit einem gewaltigen Zukunftspotential zu entwickeln.

Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates.

We report the synthesis and the reactivity of 1,2,3‐triazolin‐5‐imine type mesoionic imines (MIIs). The MIIs are accessible by a base‐mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O‐stretching frequencies in MII−CO2 and −Rh(CO)2Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N‐heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent‐induced fluorine‐specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π‐donor and π‐acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.

Structural, Electronic, Thermodynamic, Optical and Nonlinear Optical Properties of Curcumin Complexes with Transition Metals: DFT and TD‐DFT Study

AbstractBecause of their important photonic applications, the curcumin molecules, which can easily be found in nature, are interesting in the study of nonlinear optical (NLO) properties. Density functional theory (DFT) calculations on ground state molecular geometries of [(bpy‐CH3)M(curc)] Cl complexes, where M=Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Tc, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au and Hg, have been performed at B3LYP level. Most complexes have a pyramidal geometry with square base, with a few exceptions well understood from the electronic structure of the metal atom. Although the pyramid geometry with square base of the [(bpy‐CH3)Zn(curc)] Cl complex is preserved in solution, our DFT calculations show that the Zn lying above the square plane becomes closer and closer to that plane when the solvent is more and more polar, whereas the dipole moment increases in the mean time. The calculated IR spectra for the Zn complex show an increase in the intensity of the peaks of solvated complexes. The effect of solvent on excitation transition types and electronic spectra of the transition metal complexes simulated using DFT‐CPCM model shows intra‐ligand charge transfer from HOMO to LUMO in polar solvents, but from HOMO to LUMO+1 in apolar solvents. Among a full set of properties of transition metal series complexes with 21 elements, it appears that the Mn, Ag and Re complexes are the best candidates to NLO materials. Finally, an excellent correlation between the magnetic moments per atom and the number of valence electron of the central metals is obtained.

Electrodeposition of Ni–Sn alloy from ethylene glycol electrolyte. Part 2. Reactions in the bulk electrolyte

ABSTRACT Previously, the authors developed a stable citrate ethylene glycol (EG) electrolyte providing the electrodeposition of Ni–Sn alloy at quite high rate, current efficiency and nickel content in the alloy. In this study a complexation in the solution containing nickel and tin(II) chlorides, and citric acid was studied. IR spectroscopy data have shown the availability of Ni(EG)2Cl2 and Sn(EG)Cl2 complex compounds in the EG solution. At the addition of citric acid complexation of Ni(II) and Sn(II) with dihydrocitrate ions occurs. Binding of Sn(II) ions into complex compounds like Sn(EG)(H2Cit)2 promotes regulation of Ni(II) and Sn(II) reduction rates, and ensures the increased nickel quota in the alloy and the stability of electrolyte against Sn(II) to Sn(IV) oxidation. The rate of coating deposition strongly depends on the electrical conductivity of the EG solution and rises with an increase in the temperature and concentration of metal halide crystalline hydrates.

Acceptorless Dehydrogenative Cross-Coupling of Primary Alcohols Catalyzed by an N-Heterocyclic Carbene-Nitrogen-Phosphine Chelated Ruthenium(II) Complex.

The acceptorless dehydrogenative cross-coupling of primary alcohols to form cross-esters with the liberation of H2 gas was enabled using a [RuCl(η6-C6H6)(κ2-CNP)][PF6]Cl complex as the catalyst. This sustainable protocol is applicable to a broad range of primary alcohols, particularly for the sterically demanding ones, featuring good functional group tolerance and high selectivity. The good catalytic performance can be attributed to the nitrogen-phosphine-functionalized N-heterocyclic carbene (CNP) ligand, which adopts a facial coordination mode as well as the facile dissociation of coordinated benzene.

New trans-[Ru(NO)(NO2)(dppb)(o-bdqi)]+ complex as NO donor encapsulated Pluronic F-127 micelles

Ruthenium complexes that act as nitric oxide (NO) donors show potential cytotoxicity in tumor models. In this work, we proposed the synthesis of the new nitrosyl ruthenium complex trans-[Ru(NO2)(NO)(dppb)(o-bdqi)]Cl2, containing a non-innocent ligand of the o-phenylenediamine type (o-bdqi). The 31P{1H} NMR spectra confirmed that the trans-[Ru(NO2)(NO)(dppb)(o-bqdi)] is the isomer formed. The complex was characterized by elemental analysis, mass spectrometry, UV–vis and infrared spectroscopy and cyclic voltammetry. Natural transition orbitals (NTOs) for trans-[RuCl2(dppb)(o-bdqi)] and trans-[Ru(NO2)(NO)(dppb)(o-bdqi)]Cl2 complex were obtained with TD-DFT/B3LYP methodology to contribute to the assignment of electronic transition. A micellar system (F-127/Ru) produced with Pluronic F-127 copolymer was used as a drug delivery system, due to the hydrophobicity of the complex. The F-127/Ru system showed NO release in aqueous media. The free complex showed higher cytotoxicity than the F-127/Ru system in the studied tumor cells. However, the F-127/Ru system showed a higher selectivity index for lung cells. This shows that the Pluronic F-127 carrier can be a good alternative in the use of hydrophobic nitrosyl ruthenium compounds in the treatment of some types of cancer.

Speciation and thermodynamic properties of La(III)-Cl complexes in hydrothermal fluids: A combined molecular dynamics and in situ X-ray absorption spectroscopy study

Chlorine is the most common ligand in geofluids, and one of the most important complexing agents for rare earth elements. The geometry and thermodynamic properties of La(III)-Cl complexes determined by previous experimental studies show inconsistency especially at temperature over 350 °C. Here, ab initio molecular dynamics (MD) simulations were employed to determine the nature and thermodynamic properties of La(III)-Cl complexes at temperature up to 500 °C and pressure up to 30kbar. The simulations were ground proofed by in situ X-ray absorption spectroscopy (XAS) results (400 bar, 25 to 500 °C). Both MD and XAS show an increase in the relative stabilities of chloride complexes with increasing temperature. The formation constants of LaCln3-n (n = 1–3) complexes were calculated using trmodynamic integration method that is within ab initio MD. The calculated formation constants of LaCl2+ and LaCl2+ at temperatures below 400 °C agree with Migdisov et al.’s (2009) extrapolations from the Helgeson-Kirkham-Flowers (HKF) equation-of-state. We fitted the HKF equation-of-state parameters of LaCln3-n (n = 1–3) within the Deep Earth Model (DEW, Sverjensky et al., 2014) to enable the calculations of the formation constants up to 1200 °C, 60 kbar, based on the previous experimental data and the new results. The predictions confirm the increased stability of chloride complexes with increasing temperature and further underline the effect of pressure on La speciation: while LaCl3(aq) becomes important in Cl-rich metamorphic and magmatic hydrothermal fluids (T > 350 °C; P < 5kbar) circulating in the upper crust, LaCl2+ and LaCl2+ appear to be the dominant complexes under higher pressure characteristic of the lower crust or subducting slab environments.

Synthesis of a novel nitrogen mustard–conjugated bis-terpyridine ruthenium(II) complex as a potent anticancer agent that induces cell cycle arrest and apoptosis

A fairly small-sized aryl nitrogen mustard–conjugated terpyridine is synthesized in only two steps as a ligand to chelate with RuCl3 to afford a [Ru(tpy-CM)2]Cl2 complex. This complex exhibits prominent antiproliferative activity toward several tumor cells. Further studies conclusively show that the complex suppresses human renal clear cell carcinoma cells (786-O cells) by inducing G1 phase cell cycle arrest and apoptosis. This work provides a synthetic and therapeutic model for nitrogen mustard-containing metal complexes.

Substitution of the chlorido ligand for PPh3 in anticancer organoruthenium complexes of sulfonamide-functionalized pyridine-2-carbothioamides leads to high cytotoxic activity

The functionalization of Ru(arene) complexes with bioactive moieties is a promising approach for modulating their biological properties. This strategy may result in compounds with synergistic biological effects which may be capable of overcoming major drawbacks of currently used chemotherapeutics. A series of RuII(η6-p-cymene)Cl complexes 1a–1c comprising sulfonamide and pyridine-2-carbothioamide (PCA) ligands were designed to evaluate their antiproliferative potency in cancer cells. The ligands and their corresponding organoruthenium complexes were characterized by NMR spectroscopy, elemental analysis, ESI-MS analysis and the molecular structure of 1a was determined by X-ray diffraction analysis. In vitro cytotoxic assays showed that the chlorido complexes 1a–1c are inactive. However, the cytotoxicity was significantly improved when the labile chlorido ligand was replaced with triphenylphosphine in 2a–2c. The most active complex 2c showed IC50 values as low as 1.9 ± 0.5 µM in cervical carcinoma SiHa cells compared to 3.0 ± 1.1 µM for the chemotherapeutic agent cisplatin.

Halogenated β‐diketiminato magnesium complexes: Preparation, characterization, and catalysis for ring‐opening polymerization of aliphatic lactones

AbstractThe halogenated β‐diketiminato magnesium butyl complexes LXMgBu(THF) (X = Cl (1), Br (2)) and allyl complexes LXMg(allyl)(THF) (X = Cl (3), Br (4)) (LCl = ((2,6‐Cl2C6H3)N═C(Me)CH═C(Me)N(2,6‐Cl2C6H3)), LBr = ((2,6‐Br2C6H3)N═C(Me)CH═C(Me)N(2,6‐Br2C6H3)) were prepared and characterized. The treatment of butyl complex 2 with (S)‐1‐phenylethanol gave the corresponding alkoxide complex [LBrMgOCHMePh]2 (5), the dimeric structure of which was confirmed by single‐crystal x‐ray diffraction. When bulky diphenylmethanol was employed to react with Complex 2, THF‐ligated monomeric complex LBrMgOCHPh2(THF) (6) was afforded. The catalytic performances of these magnesium complexes for ring‐opening polymerization of ε‐caprolactone (ε‐CL), δ‐valerolactone (δ‐VL), and γ‐butyrolactone (γ‐BL) were evaluated.

Synthesis, Characterization, Thermal Analysis, DFT, and Cytotoxicity of Palladium Complexes with Nitrogen-Donor Ligands.

Three new palladium complexes ([Pd(DABA)Cl2], [Pd(CPDA)Cl2], and [Pd(HZPY)Cl2]) bearing dinitrogen ligands (DABA: 3,4-diaminobenzoic acid; CPDA: 4-chloro–o-phenylenediamine; HZPY: 2-hydraziniopyridine) were synthesized, characterized, and tested against breast cancer (MCF-7), prostate carcinoma cell line (PC3) and liver carcinoma cell line (HEPG2). [Pd(DABA)Cl2] complex exhibited the highest inhibition percentage, lying between 68–71%. The hydrolysis mechanism of each palladium complex, the key step preceding the binding to the biological target, as well as their photophysical properties were explored by means of DFT and TDDFT computations. Results indicate a faster hydrolysis process for the Pd(DABA)Cl2 complex. The computed activation energies for the first and second hydrolysis processes suggest that all the compounds could reach DNA in their monohydrated form.

Probing the interaction of new and biologically active Pd(II) complex with DNA/BSA via joint experimental and computational studies along with thermodynamic, NLO, FMO and NBO analysis.

Treatment with transition metal complexes is an efficient method to fight with cancer. Therefore, a new transition metal complex formulated as [Pd(1, 3-pn)(acac)]Cl (pn and acac stand for propylendiamine and acetylacetonate, respectively) was synthesized and analyzed using 1H NMR, Fourier transform infrared, electronic absorption spectroscopy techniques as well as elemental analysis and conductivity measurement. The geometry optimization, frontier molecular orbital (FMO) analysis, molecular electrostatic potential (MEP), natural bond orbital (NBO) analysis and nonlinear optical (NLO) property were accomplished by density functional theory (DFT) at B3LYP level with 6-311G(d,p)/aug-cc-pVTZ-PP basis set. Preliminary determination of antitumor activity and lipophilicity of this metal complex was performed experimentally and the promising results were obtained. This encouraged us to study the interaction and binding mode/modes of this complex with DNA as the primary receptor for the chemotropic drugs and BSA as the transporter protein in the circulatory system. For this reason, the binding of newly made complex was assessed in-vitro under physiological state using experimental and in-silico molecular modeling studies. So, the CT-DNA binding study of this complex was explored using spectrofluorometric as well as spectrophotometric techniques, viscosity and gel electrophoresis experiments. Furthermore, fluorescence, UV-Vis, F[Formula: see text]rster resonance energy transfer and circular dichroism studies were carried out for BSA binding. The experimental and computational interaction studies showed that [Pd(1, 3-pn)(acac)]Cl complex binds to the minor groove of CT-DNA and interacts with BSA by van der Waals forces and hydrogen bond.