An insight into the morphology of DNA compaction induced by homobinuclear Ru(II) polypyridyl complexes.

Binuclear Ru(II) polypyridyl complexes [Ru2(NN)4(BIPMB)]4+ (1-4), where N-N = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), dipyrido [3,2-d:2',3'-f] quinoxaline (dpq), and dipyrido[3,2-a:2',3'-c]phenazine (dppz), have been synthesized using suitable precursors and bridging ligand (BIPMB), where BIPMB = 3,3'-bis-{(imidazol-1-yl)-[4,5-f]-1,10-phenanthroline) methyl}-1,1'-biphenyl. The binding mode and affinity of complexes 1-4 with Calf Thymus DNA (CT-DNA) were determined by absorption and steady-state fluorescence spectroscopy. The decrease in viscosity of CT-DNA on sequential addition of these complexes indicated DNA condensation and the result was corroborated by circular dichroism (CD). The nanosized globular aggregates of CT-DNA induced by complexes 1-4 were observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements. The gel electrophoretic mobility studies revealed the small orderly particles of supercoiled plasmid pBR322 DNA induced by these complexes. Additionally, the morphology and size of compact plasmid DNA condensates were studied by DLS and atomic force microscopy (AFM). The complexes were moderately cytotoxic against MCF-7 cells.

Tris-heteroleptic ruthenium(II) polypyridyl complexes: Synthesis, structural characterization, photophysical, electrochemistry and biological properties.

Three water-soluble tris-heteroleptic ruthenium(II) polypyridyl complexes [Ru(bpy)(phen)(bpg)]2+ (1), [Ru(bpy)(dppz)(bpg)]2+ (2), and [Ru(phen)(dppz)(bpg)]2+ (3) (where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2',3'-c] phenazine, bpg = 4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f] [1,10] phenanthroline-6,13-dione) have been synthesized and characterized. Molecular structures of complexes 1 and 3 are confirmed by single crystal X-ray structure determination. Interaction of complexes 1-3 with DNA is explored by various spectroscopic techniques. The complexes 1-3 show solvent dependent photophysical properties. Complexes 2 and 3 show extensive "molecular light switch" effect for DNA. The complexes 1-3 are low toxic towards HeLa (human cervical cancer) and HL-60 (human promyelocytic leukemia) cell lines. Further, the cellular uptake of complexes 2 and 3 by cells shows that complexes mainly localised on the nucleus of the cells.

Heterostructural CuO-ZnO Nanocomposites: A Highly Selective Chemical and Electrochemical NO2 Sensor.

A simple one-step chemical method is employed for the successful synthesis of CuO(50%)-ZnO(50%) nanocomposites (NCs) and investigation of their gas sensing properties. The X-ray diffraction studies revealed that these CuO-ZnO NCs display a hexagonal wurtzite-type crystal structure. The average width of 50-100 nm and length of 200-600 nm of the NCs were confirmed by transmission electron microscopic images, and the 1:1 proportion of Cu and Zn composition was confirmed by energy-dispersive spectra, i.e., CuO(50%)-ZnO(50%) NC studies. The CuO(50%)-ZnO(50%) NCs exhibit superior gas sensing performance with outstanding selectivity toward NO2 gas at a working temperature of 200 °C. Moreover, these NCs were used for the indirect evaluation of NO2 via electrochemical detection of NO2 - (as NO2 converts into NO2 - once it reacts with moisture, resulting into acid rain, i.e., indirect evaluation of NO2). As compared with other known modified electrodes, CuO(50%)-ZnO(50%) NCs show an apparent oxidation of NO2 - with a larger peak current for a wider linear range of nitrite concentration from 20 to 100 mM. We thus demonstrate that the as-synthesized CuO(50%)-ZnO(50%) NCs act as a promising low-cost NO2 sensor and further confirm their potential toward tunable gas sensors (electrochemical and solid state) (Scheme 1).

Photochemical hydrogen evolution from water by a 1D-network of octahedral Ni6L8 cages.

A self-assembled M6L8 type cage-connected 1D-coordination network of formula {[Ni6(MeSi(3py)3)8Cl9(H2O)2]Cl3·16H2O}∞ (1) was obtained from a 3-pyridyl substituted silane ligand MeSi(3py)3. This complex shows significantly high performance for the electrocatalytic and photocatalytic hydrogen evolution reaction (HER) in water. A maximum turnover number (TON) of 2824 has been observed for photocatalytic HER after 69 h.

Coordination polymers of CdII and PbII derived from bipyridine-glycoluril: influence of metal-ion size and counter-ions.

Two new one-dimensional (1D) coordination polymers (CPs), namely catena-poly[[[aquacadmium(II)]-bis(µ-4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione)] bis(perchlorate) dihydrate], {[Cd(C14H10N6O2)2(H2O)](ClO4)2·2H2O}n or {[Cd(BPG)2(H2O)](ClO4)2·2H2O}n, 1, and catena-poly[[lead(II)-bis(µ-4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione)] bis(perchlorate) dihydrate], {[Pb(C14H10N6O2)2](ClO4)2·2H2O}n or {[Pb(BPG)2](ClO4)2·2H2O}n, 2, have been synthesized using bipyridine-glycoluril (BPG; systematic name: 4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione), a urea-fused tecton, in a mixed-solvent system. The CdII ion in 1 is heptacoordinated and the PbII ion in 2 is hexacoordinated, with the CdII ion adopting a pentagonal bipyramidal geometry and the PbII ion adopting a distorted octahedral geometry. Both CPs form infinite linear chain structures which are hydrogen bonded to each other leading to the formation of three-dimensional supramolecular network structures. Topological analysis of CPs 1 and 2 reveals that the structures exhibit 1D chain-like arrangements in an AB-AB sequence and shows platonic uniform 2-connected uninodal topologies. Furthermore, a comparative analysis of a series of structures based on the BPG ligand indicates that the size of the metal ion and the types of counter-ions used have a great influence on the resulting frameworks and properties.

A copper(ii)-coordination polymer based on a sulfonic-carboxylic ligand exhibits high water-facilitated proton conductivity.

Proton conduction ability has been investigated in a new Cu(ii) based coordination polymer (CP), {[Cu2(sba)2(bpg)2(H2O)3]·5H2O}n (1), synthesized using the combination of 4-sulfobenzoic acid (4-Hsba) and bipyridine-glycoluril (BPG) ligands. Single crystal X-ray structure determination revealed that 1 features 1D porous channels encapsulating a continuous array of water molecules. Proton conductivity measurements reveal a high conductivity value of 0.94 × 10-2 S cm-1 at 80 °C and 95% RH. The activation energy (Ea) of 0.64 eV demonstrates that the solvate water, coordinated water and hydrophilic groups in the channels promote the mobility of protons in the framework. Water sorption measurements exhibited hysterical behaviour with a high uptake value of 379.07 cm3 g-1. Time-dependent measurements revealed that the proton conductivity is retained even after 12 h of measurements. The proton conduction mechanism was validated by ab initio electronic structure calculations using the Nudged Elastic Band (NEB) method with molecular dynamics (MD) simulation studies. The theoretical activation energy is calculated to be 0.54 eV which is in accordance with the experimental value.

Acetylcholinesterase and Aß Aggregation Inhibition by Heterometallic Ruthenium(II)-Platinum(II) Polypyridyl Complexes.

Two heteronuclear ruthenium(II)-platinum(II) complexes [Ru(bpy)2(BPIMBp)PtCl2]2+ (3) and [Ru(phen)2(BPIMBp)PtCl2]2+ (4), where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and BPIMBp = 1,4'-bis[(2-pyridin-2-yl)-1H-imidazol-1-ylmethyl]-1,1'-biphenyl, have been designed and synthesized from their mononuclear precursors [Ru(bpy)2(BPIMBp)]2+ (1) and [Ru(phen)2(BPIMBp)]2+ (2) as multitarget molecules for Alzheimer's disease (AD). The inclusion of the cis-PtCl2 moiety facilitates the covalent interaction of Ru(II) polypyridyl complexes with amyloid ß (Aß) peptide. These multifunctional complexes act as inhibitors of acetylcholinesterase (AChE), Aß aggregation, and Cu-induced oxidative stress and protect neuronal cells against Aß-toxicity. The study highlights the design of metal based anti-Alzheimer's disease (AD) systems.

Excited State Interaction of Ruthenium (II) Imidazole Phenanthroline Complex [Ru(bpy)2 ipH]2+ with 1,4-Benzoquinone: Simple Electron Transfer or Proton-Coupled Electron Transfer?

The unidirectional proton coupled electron transfer (PCET) from the excited state of Ru(II) imidazole phenanthroline complex [Ru(bpy)2 ipH]2+ to 1,4-benzoquinone, was studied by steady-state (SS) and time-resolved (TR) fluorescence and transient absorption (TA) measurements. The pKa (9.7) and pKa * (8.6) values of the complex suggest that it behaves as a photoacid on excitation. The difference in the quenching rates obtained from SS and TR fluorescence studies indicate participation of both dynamic quenching and static quenching involving the hydrogen bonded ipH ligand of [Ru(bpy)2 ipH]2+ with the 1,4-benzoquinone quencher, formed in the ground state. Within the hydrogen bonded complex, the ruthenium centre acts as the electron donor, while the ipH ligand acts as the proton donor to the hydrogen bonded 1,4-benzoquinone that acts simultaneously both as the electron and proton acceptor. It is proposed that the static quenching in the hydrogen bonded [Ru(bpy)2 ipH]2+ -1,4-benzoquinone pairs occurs involving the PCET mechanism, while the dynamic quenching occurs through the simple ET mechanism, on diffusional encounter of the isolated 1,4-benzoquinone with the excited [Ru(bpy)2 ipH]2+ complex. The occurrence of broad TA bands around 420-430 nm suggests formation of both 1,4-benzoquinone radical anion as well as the 1,4-benzosemiquinone radical by the interaction of excited [Ru(bpy)2 ipH]2+ with 1,4-benzoquinone, thus supporting the ET process in the studied system.

Light-driven Hydrogen Evolution from Water by a Tripodal Silane Based CoII6L18 Octahedral Cage.

The octahedral cage assembly [CoII6L18Cl6(H2O)6]Cl6 has been synthesized in a single-step reaction by using a polypyridyl-functionalized tripodal silane ligand. The electrochemical behavior of the cage in water exhibits the pH dependence of potential as well as catalytic current indicating the possible involvement of proton-coupled electron transfer in H2 evolution. Electrocatalytic hydrogen evolution from an aqueous buffered solution gave a turnover frequency of 16 h-1. Further, this cage assembly has been explored as a photocatalyst (blue light irradiation λ 469 nm) for the evolution of H2 from water in the presence of Ru(bpy)32+ as a photosensitizer and ascorbic acid as a sacrificial electron donor. This catalytic reaction is found to be pseudo first order with a turnover frequency of 20.50 h-1.

A ruthenium water oxidation catalyst containing a bipyridine glycoluril ligand.

A mononuclear ruthenium complex [Ru(tpy)(bpg)H2O]2+ bearing a bipyridine glycoluril where bpg = 4b,5,7,7a-tetrahydro-4b,7a-nepiminomethanoimino-6H-imidazo[4,5-f][1,10]phenanthro-line-6,13-dione acts as a robust water oxidation catalyst (WOC) at pH = 1 using Ce(iv) as a sacrificial oxidant. The turn over number (TON) for water oxidation is found to be ∼5 times higher than the parent complex [Ru(tpy)(bpy)H2O]2+ where tpy = 2,2':6',2''-terpyridine; bpy = 2,2'-bipyridine. The presence of intermolecular H-bonding groups and the electronic effect of the functionalized bipyridine ligand may play a significant role in water oxidation.

Proton conduction in a hydrogen-bonded complex of copper(ii)-bipyridine glycoluril nitrate.

Bipyridine glycoluril (BPG), a urea-fused bipyridine tecton, forms a square-pyramidal secondary building unit with copper(ii) which further self-assembles to give a porous hydrogen-bonded complex. This complex displays a high proton conductivity of 4.45 × 10-3 S cm-1 at 90 °C and 95% relative humidity (RH). Chains consisting of coordinated water, solvent water and nitrate anions embedded in the complex are responsible for high proton conduction. The proton conduction pathway was corroborated by ab initio electronic structure calculations with molecular dynamics (MD) simulations using the Nudged Elastic Band (NEB) method. The theoretical activation energy estimated to be 0.18 eV is in close agreement with the experimental value of 0.15 eV which evidences a Grotthuss proton hopping mechanism. We thus demonstrate that the hydrogen-bonded complex encapsulating appropriate counter ions, coordinated water and solvent water molecules exhibts superprotonic conductivity.

Honeycomb-like Ordered Assembly of DNA Induced by Flexible Binuclear Ruthenium(II)-Polypyridyl Complexes.

A series of binuclear ruthenium(II)-polypyridyl complexes of the type [Ru2 (N-N)4 (BPIMBp)]4+ , in which N-N is 2,2'-bipyridine (bpy; 1), 1,10-phenanthroline (phen; 2), dipyrido[3,2-d:2',3-f] quinoxaline (dpq; 3), dipyrido[3,2-a:2',3'-c] phenanzine (dppz; 4), and 1,4'-bis[(2-pyridin-2-yl)-1H-imidazol-1-yl)methyl]-1,1'-biphenyl (BPIMBp) is a bridging ligand, have been synthesized and characterized. These complexes are charged (4+) cations and flexible due to the -CH2 group of the bridging ligand and possess terminal ligands with variable intercalative abilities. The interaction of complexes 1-4 with calf thymus DNA (CT-DNA) was explored by using UV/Vis absorption spectroscopy, steady-state emission, emission quenching with K4 [Fe(CN)6 ], ethidium bromide displacement assay, Hoechst displacement assay, and viscosity measurements and revealed a groove-binding mode for all the complexes through a spacer and an intercalative mode for complexes 3 and 4. A decrease in the viscosity of DNA revealed bending and coiling of DNA, an initial step toward aggregation. Interestingly, a distinctive honeycomb-like ordered assembly of the DNA-complex species was visualized by fluorescence microscopy in the solution state. The use of SEM and AFM confirmed the disordered self-organization of the DNA-complex adduct on evaporation of the solvent. The small orderly nanosized DNA aggregates were confirmed by means of circular dichroism, dynamic light scattering (DLS), and TEM. These complexes are moderately cytotoxic against three different cell lines, namely, MCF-7, HeLa, and HL-60.

Ruthenium(II) polypyridyl complexes with hydrophobic ancillary ligand as Aß aggregation inhibitors.

The synthesis, spectral and electrochemical characterization of the complexes of the type [Ru(NN)2(txbg)](2+) where NN is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), dipyrido [3,2-d:2',3f] quinoxaline (dpq) (3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4) which incorporate the tetra-xylene bipyridine glycoluril (txbg) as the ancillary ligand are described in detail. Crystal structures of ligand txbg and complex 2 were solved by single crystal X-ray diffraction. Thioflavin T (ThT) fluorescence and Transmission Electron Microscopy (TEM) results indicated that at micromolar concentration all complexes exhibit significant potential of Aß aggregation inhibition, while the ligand txbg displayed weak activity towards Aß aggregation. Complex 1 showed relatively low inhibition (70%) while complexes 2-4 inhibited nearly 100% Aß aggregation after 240 h of incubation. The similar potential of complexes 2-4 and absence of any trend in their activity with the planarity of polypyridyl ligands suggests there is no marked effect of planarity of coligands on their inhibitory potential. Further studies on acetylcholinesterase (AChE) inhibition indicated very weak activity of these complexes against AChE. Detailed interactions of Aß with both ligand and complex 2 have been studied by molecular modeling. Complex 2 showed interactions involving all three polypyridyl ligands with hydrophobic region of Aß. Furthermore, the toxicity of these complexes towards human neuroblastoma cells was evaluated by MTT assay and except complex 4, the complexes displayed very low toxicity.

Antiproliferative activity of ruthenium(ii) arene complexes with mono- and bidentate pyridine-based ligands.

A series of Ru(II) arene complexes of mono- and bidentate N-donor ligands with carboxyl or ester groups and chlorido ancillary ligands were synthesised and structurally characterised. The complexes have a distorted tetrahedral piano-stool geometry. The binding interaction was studied with calf thymus DNA (CT-DNA) by absorption titration, viscosity measurement, thermal melting, circular dichroism, ethidium bromide displacement assay and DNA cleavage of plasmid DNA (pBR322), investigated by gel electrophoresis. The dichlorido complexes bind covalently to DNA in the dark, similar to cisplatin, while the monochlorido complexes bind covalently on irradiation, similar to cisplatin analogues. The compounds are selectively cytotoxic against several tumour cell lines and show specific nonlinear correlation between dose and activity. This phenomenon is closely related to their potential to act preferentially as inhibitors of cell division.

Copper(ii) mixed-ligand polypyridyl complexes with doxycycline - structures and biological evaluation.

Mixed-ligand Cu(ii) complexes of the type [Cu(doxycycline)(L)(H2O)2](NO3)2, where doxycycline = [4-(dimethylamino)-3,5,10,12,12a-pentahydroxy-6-methyl-1,11-dioxo-1,4,4a,5,5a,6,11,12a-octahydrotetracene-2-carboxamide] and L = 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 3) and dipyrido[3,2-a:2',3'-c]phenazine (dppz, 4) have been synthesised and characterised by structural, analytical, and spectral methods. The single-crystal X-ray structures of 1 and 2 exhibited two different geometries, distorted square-pyramidal and octahedral respectively as well as different coordination modes of doxycycline. Complexes 2-4 exhibit prominent plasmid DNA cleavage at significantly low concentrations probably by an oxidative mechanism. Matrix Metalloproteinase (MMP-2) inhibition studies revealed that all complexes inhibit MMP-2 similar to doxycycline which is a well-known MMP inhibitor with 3 being the most potent. IC50 values of doxycycline and 1-4 against MCF-7 (human breast cancer) and HeLa cell lines were almost equal in which 3 showed the highest efficiency (IC50 = 0.46 ± 0.05 µM), being consistent with its increased MMP inhibition potency. The antimalarial activities of these complexes against the chloroquine-sensitive Plasmodium falciparum NF54 and chloroquine-resistant Plasmodium falciparum Dd2 strains reveal that complex 3 exhibited a higher activity than artesunate drug against the chloroquine-resistant Dd2 strain.

Ruthenium(II) polypyridyl complex as inhibitor of acetylcholinesterase and Aß aggregation.

Two ruthenium(II) polypyridyl complexes [Ru(phen)3](2+) (1) and [Ru(phen)2(bxbg)](2+) (2) (where phen = 1,10 phenanthroline, bxbg = bis(o-xylene)bipyridine glycoluril) have been evaluated for acetylcholinesterase (AChE) and Amyloid-ß peptide (Aß) aggregation inhibition. Complex 2 exhibits higher potency of AChE inhibition and kinetics and molecular modeling studies indicate that ancillary ligand plays significant role in inhibitory potency exhibited by complex 2. The inhibitory effect of these complexes on Aß (1-40) aggregation is investigated using Thioflavin T fluorescence and Transmission Electron Microscopy. Both complexes efficiently inhibit Aß (1-40) aggregation and are negligibly toxic to human neuroblastoma cells. This is the first demonstration that ruthenium(II) polypyridyl complexes simultaneously inhibit AChE and Aß aggregation.

Efficient DNA condensation induced by ruthenium(II) complexes of a bipyridine-functionalized molecular clip ligand.

Complexes of the type [Ru(bxbg)(2) (N-N)](2+), where N-N denotes 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), dipyrido[3,2-d:2',3-f] quinoxaline (dpq) (3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4), incorporating bis(o-xylene)bipyridine-glycoluril (bxbg) as an ancillary "molecular clip" ligand, have been synthesized and characterized. These ruthenium(II) complexes of bis(o-xylene)bipyridine-glycoluril self-associate in water through specific molecular recognition processes to form polycationic arrays. These arrays containing electrostatic binders as well as intercalator ligands at micromolar doses rapidly condense free DNA into globular nanoparticles of various sizes. The DNA condensation induced by these complexes has been investigated by electrophoretic mobility assay, dynamic light scattering, and transmission electron microscopy. The cellular uptake of complex-DNA condensates and the low cytotoxicity of these complexes satisfy the requirements of a gene vector.

Ruthenium(II) polypyridyl complexes as carriers for DNA delivery.

Two novel water soluble ruthenium(II) complexes [Ru(bpy)(2)(bqbg)](2+) and [Ru(phen)(2)(bqbg)](2+) have been structurally characterized and their DNA condensation activity, cytotoxicity, and cellular uptake studies of DNA condensates as potential non-viral DNA carriers were evaluated.

Mixed ligand cobalt(II) picolinate complexes: synthesis, characterization, DNA binding and photocleavage.

Complexes of the type [Co(pic)(2)(NN)], where pic = picolinate, NN = dipyrido[3,2-d:2',3'-f]quinoxaline (dpq) (4) and 4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f][1,10]-phenanthroline-6,13-dione (bipyridyl-glycoluril) (bpg) (6) have been synthesized and characterized by elemental analysis, IR, UV-vis, NMR and ESI-MS spectroscopy and thermogravimetic analysis (TGA). Their physicochemical properties are compared with previously synthesized complexes, where NN = (H(2)O)(2) (1), 2,2'-bipyridine (bpy) (2), 1,10-phenanthroline (phen) (3) and dipyrido[3,2-a:2',3'-c]phenazine (dppz) (5). The crystal structures of the complexes 4-6 were solved by single-crystal X-ray diffraction. The complexes 4 and 5 crystallize from a mixture of chloroform and methanol in monoclinic and orthorhombic crystal systems, respectively, whereas complex 6 crystallizes from dimethyl sulfoxide (DMSO) in a tetragonal crystal system. The coordination sphere consists of two oxygen atoms and two nitrogen atoms from the two picolinates and two nitrogen atoms from the dpq, dppz or bpg ligand, respectively. Co(ii)/Co(iii) oxidation potentials have been determined by cyclic voltammetry. The DNA binding of complexes 1-5 has been investigated using thermal melting, fluorescence quenching and viscosity measurements, which indicate the partial intercalation of complex 5 with an apparent binding constant (k(app)) of 8.3 × 10(5) M(-1). DNA cleavage studies of complexes 1-5 have been investigated using gel electrophoresis in the presence of H(2)O(2) as an oxidizing agent and also by photoirradiation at 365 nm. The mechanistic investigations suggest that singlet oxygen ((1)O(2)) is the major species involved in the DNA cleavage by these complexes. The structures of complexes 2-6 were optimized with density functional theory (DFT) method (B3LYP/6-31G(d,p)). The low vertical ionization potential values indicate photoredox pathways for the DNA cleavage activity by complexes 4 and 5, which is corroborated by DNA cleavage experiments.

Stabilization of acyclic water tetramer in a copper(II) malonate framework structure.

Copper(II) complex [Cu(dpq)(mal)(H(2)O)]·3H(2)O (1) (dpq = dipyrido-[3,2-d:2',3'-f]-quinoxaline, mal = malonato) was synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray crystallography. The single-crystal X-ray structure of 1 reveals a square pyramidal structure, with the dipyrido-[3,2-d:2',3'-f]-quinoxaline and malonato at the equatorial positions and a water molecule at the axial position. The molecule acts as a building block generating a supramolecular three-dimensional metal-organic framework (MOF) encapsulating metal linked acyclic water tetramer. The H-bonding capacity of malonato and the π-π stacking interactions of dipyrido-[3,2-d:2',3'-f]-quinoxaline further reinforce the framework. The copper(II) bound hydroxyl group is demonstrated to mediate hydrolytic cleavage of plasmid pBR322 DNA under dark conditions.