Three bridged dinuclear complexes [Cu-2(dien)(2)(mu-4,4`-bpe)(ClO4)(4)] (1), [Cu-2(dien)(2)(mu-4,4`-bpe)(dca)(2)](ClO4)(2) (2) and [Cu-2(HL)(2)(mu-4,4`-bpe)(DMF)center dot 2DMF (3), and the coordination polymer catena-[Cu(N,N,N '-Et(3)en)(mu-1,5-dca)(dca)] (4), where 4,4`-bpe = 1,2-bis(4-pyridyl)ethane, dca = dicyanamide anion, dien = diethylenetriamine, N,N,N`-Et(3)en = N,N,N`-triethylethylenediamine and HL2- = the dianion Schiff base of 2-aminoterephthalic acid and salicylaldehyde, were synthesized and structurally characterized. The least common coordination sphere properties of the polymeric complex 4, in which two dca molecules exists, one is mono-dentate coordinated to the Cu(II) ions through a terminal dca nitrile and the second one is bridging the copper centers via mu-1,5-dca bonding across the {Cu(L)(dca)(mu-1,5-dca)Cu(L)} fragments, are explored and compared to other related published compounds.

Two doubly bridged hydroxido cobalt(III) complexes [(TPA)Co(mu -OH)2Co(TPA)](ClO4)4 & sdot;H2O (1) and [(L)Co (mu -OH)2Co(L)]& sdot;2H2O (2) were synthesized from the tripod ligands TPA (tris(2-methypyridyl)amine) and H2L ((bis(6,6 '-(((pyridin-2-ylmethyl)azanediyl)bis(methylene))bis(2-bromo-4-methylphenol)) and structurally characterized. The six-coordinate complexes 1 and 2 are stable in air and in aqueous medium as well as exhibit reasonable solubility in water. An easy new straight forward method is reported for the synthesis of the bridged hydroxido-peroxido complex [(TPA)Co(mu 1,2-O2)(mu -OH)Co(TPA)](ClO4)3 & sdot;H2O (3), whose its coordination structural core parameters are compared to the bridged hydroxido complexes 1 and 2. The three complexes exhibit strong intense absorption band due to O-pi*-> CoIII LMCT in the visible region.

The oxazines bearing piperazinyl moieties namely 2-(tert-butyl)-6-((4-(2-(8-(tert-butyl)-6-methyl-2H-benzo[e] [1,3]oxazin-3(4H)-yl)ethyl)piperazin-1-yl)methyl)-4-methylphenol (1) and its corresponding 2,4-di-tert-butyl-6- ((4-(2-(6,8-di-tert-butyl-2H-benzo[e]-[1,3]oxazin-3(4H)-yl)ethyl)piperazin-1-yl)methyl)phenol (2), which was previously isolated were described. The transformation of the piperazinyl tri-tert-butyl-phenol derivatives 6,6 '- (((2-(4-(3-(tert-butyl)-2-hydroxy-5-methylbenzyl)piperazin-1-yl)ethyl)-azanediyl)bis-(methylene))bis-(2-(tert- butyl)-4-methylphenol) 3 and 6,6 '-(((2-(4-(3,5-di-tert-butyl-2-hydroxybenzyl)piperazin-1-yl)ethyl)-azanediyl)-bis (methylene))bis(2,4-di-tert-butyl-phenol) 4 into 1 and 2, respectively was achieved in high yield by heating and stirring a methanolic solution containing Et3N and Ga(NO3)3.6H2O in the stochiometric ratio 1:3:1 for 30 min. The novel oxazine-piperazine 1 together with its triphenol-piperazine 3 (H3L4) were structurally characterized by spectroscopic and single crystal X-ray crystallography.

Four CoII complexes [Co(L1)(MeOH)] & sdot; MeOH (1 & sdot; MeOH), [Co(L2)(MeOH)] & sdot; MeOH (2 & sdot; MeOH), [Co(L3)(H2O)] & sdot; MeOH (3 & sdot; MeOH) and [Co(L4)] (4), derived from tripodal tetradentate phenolic amine arms, H2L1-4 were synthesized and structurally characterized. The complexes 1 & sdot; MeOH, 2 & sdot; MeOH and 3 & sdot; MeOH displayed distorted trigonal bipyramidal geometry, whereas 4 exhibited distorted tetrahedral geometry, depending on the substituents at the phenolate rings and amine arm. The variation of the coordination geometries and interatomic parameters around the CoII center has an impact on the magnetic behavior of the compounds. The complexes show magnetic anisotropy (ZFS) of the MS= +/- ${\pm }$ 1/2 and and +/- ${\pm }$ 3/2 sub-levels, with D=29.1(2), 22.7(1), 28.8(2) and 30.9(5) cm-1 for 1 & sdot; MeOH, 2 & sdot; MeOH, 3 & sdot; MeOH and 4, respectively. The results obtained from ab initio CASSF calculations match well with the experimental data, revealing the origin of magnetic anisotropy. The dynamic ac magnetic investigation of the magnetic susceptibility revealed a slow magnetic relaxation behavior for 2 & sdot; MeOH, 3 & sdot; MeOH and 4. The field-induced slow relaxation of the magnetization occurred through combination of Raman and Direct processes, depending on the variation in the coordination geometries imposed by the coordinated ligand and/or the interatomic parameters around the CoII center, which in turn have definite impact on the magnetic features of the compounds.

Structurally diverse zinc( ii ) complexes with tripodal tetradentate phenolic-amines of variable substituents in the phenol and amine moieties were synthesized and thoroughly characterized.

A new series of tripodal and linear phenolic-amines as well as 1,4,7,10-tetrakis(2,4-dialky-1-hydroxy-6-benzyl)-1,4,7,10-tetraazacyclododecane were efficiently synthesized in excellent to reasonably moderate yields. The one-pot reactions were performed in methanol solution through the commercially available 2,4-disubstited-phenols and dialkyldiamines or the macrocycles 1,4,7,10-tetraazacyclododecane (cyclen) and 1,4,8,11-tetraazacyclotetradecane (cyclam) in the presence of aqueous 37 % HCHO and Et3N. All the isolated compounds were spectroscopically characterized and, in some cases, structurally determined by single crystal- X-ray crystallography.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Several multinuclear bicompartmental bis(phenolato) M( ii ) complexes were structurally and magnetically characterized.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Two cationic [Cu-2(L1-2)(2)](ClO4)(2) (1, 2), and four neutral doubly bridged-phenoxido-copper(II) complexes [Cu-2(L3-4)(2)] (3, 4) and [Cu-2(L5-6)(2)(H2O)center dot 2H(2)O (5, 6) as well as 1D polymeric catena-[Cu(L-7)] (7), where HL1-2 and H2L3-7 represent tripodal tetradentate pyridyl or aliphatic-amino groups based 2,4-disubstituted phenolates, were synthesized and thoroughly characterized by various spectroscopic methods and single crystal X-ray analysis. The molecular structures of the complexes exhibited diverse geometrical environments around the central Cu(II) atoms. The in vitro antiproliferative activity of the isolated complexes and selected parent free ligands were screened against some human cancer cell lines (A2780, A2780R, PC-3, 22Rv1, MCF-7). The most promising cytotoxicity against cancer cells were obtained for 1-6, while complex 6 was found as the best per-forming as compared to the reference drug cisplatin. The cytotoxicity study of complex 6 was therefore extended to wider variety of cancer cell lines (HOS, A549, PANC-1, CaCo2, HeLa) and results revealed its significant cytotoxicity on all investigated human cancer cells. The cell uptake study showed that cytotoxicity of 6 (3 mu M concentration and 24 h of incubation) against A2780 cells was almost independent from the intracellular levels of copper. The effect of complexes 4, 6 and 7 on cell cycle of A2780 cells indicates that the mechanism of action in these complexes is not only different from that of cisplatin but also different among them. Complex 7 was able to induce apoptosis in A2780 cells, while complexes 4 and 6 did not and on the other hand, they showed considerable effect on autophagy induction and there are some clues that these complexes were able to induce cuproptosis in A2780 cells.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Three new tripod tetradentate phenolate-amines (H2L1, H2L4 and H2L9), together with seven more already related published ligands, were synthesized, and characterized. With these ligands, two new dinuclear doubly-bridged-phenoxido copper(II) complexes (3, 4), and six more complexes (1, 2, 5–8), a new trinuclear complex (9) with an alternative doubly-bridged-phenoxido and –methoxido, as well as the 1D polymer (10) were synthesized, and their molecular structures were characterized by spectroscopic methods and X-ray single crystal crystallography. The Cu(II) centers in these complexes exhibit distorted square-pyramidal arrangement in 1–4, mixed square pyramidal and square planar in 5, 6, and 9, and distorted octahedral (5+1) arrangements in 7 and 8. The temperature dependence magnetic susceptibility study over the temperature range 2–300 K revealed moderate–relatively strong antiferromagnetic coupling (AF) (|J| = 289–145 cm−1) in complexes 1–6, weak-moderate AF (|J| = 59 cm−1) in the trinuclear complex 9, but weak AF interactions (|J| = 3.6 & 4.6 cm−1) were obtained in 7 and 8. No correlation was found between the exchange coupling J and the geometrical structural parameters of the four-membered Cu2O2 rings.

The coordination properties of the macrocycle 1,4,7,10-tetrakis(2,4-dimethyl-1-hydroxy-6-methyl-benzyl)-1,4,7,10-tetraazacyclododecane, H4LMe,Me have been investigated with lanthanides La(III) and Pr(III) and 3/4d metal ions Zn(II) and Y(III). Two Pr(III) complexes [Pr(HLMe,Me)]‧MeOH (2a) and [Pr(HLMe,Me)]‧2H2O (2b) with coordination numbers (C.N.) 7 and 8, respectively as well as the [La(HLMe,Me)]‧2H2O (1) complex, which was isomorphic with 2b were isolated. In addition, [Y(HLMe,Me)]‧CH3CN‧H2O (3) and [Zn(H3LMe,Me)](NO3) (4) with C.N. 7 and 5, respectively were synthesized too. All complexes were spectroscopically and structurally characterized as well as luminescence emission of 2a and 2b.

A novel series of Cu(II) and Zn(II) complexes were constructed through the bridging croconate (C5O5)2-, squarate (C4O4)2-and 2,5-pyridine-dicarboxylate (Py2,5-dc)2-dianions. These include pent- [Cu5(epdmpy)4(-C5O5)2(H2O)6](ClO4)6 center dot 12H2O (1) and tri-nuclear [Cu3(bepza)2(Py2,5-dc)2(ClO4)2(H2O)2]center dot 2H2O (4), dinuclear [Zn2(MeDPA)2(C4O4)(H2O)4](ClO4)2 (7), and 1-D-coordination polymers (CPs) catena-{[Cu2(bpzpy)2(C5O5)] (ClO4)2 center dot MeOH} (2) and catena-{[Zn(4,4 '-bipy)(H2O)4](C5O5)(H2O)} (6) as well as the mononuclear [Cu (HBph2,2 '-dc)(pmdien)]ClO4 (5) have been synthesized and spectroscopically characterized as well as by single crystal X-ray crystallography. The reaction of aqueous solution Cu(ClO4)2, pymeea and C5O52-resulted in the unprecedently bis(oxalato) [Cu2(Pymeea)2(C2O4)(ClO4)2(H2O)2] (3). In these complexes, (C5O5)2-, squarate (C4O4)2-and (Py2,5-dc)2-ligands display a variety of coordination bonding modes. In complexes 1 and 2 the croconato is binding as 1,2-bidentate-3-monodentate but in addition 5-mono-dentate semi-coordinate bonding was detected for 2, whereas in 6 as counter dianion. The bonding mode in the squarato 7 was achieved through the trans mu 1,3-mono-dentate. In the di-carboxylato compounds, only five-membered chelate ring was formed in 5 via one of the carboxylate groups, whereas in 4 bridging was conducted through a mono-carboxylate and five -membered chelate ring including the second carboxylate and pyridyl nitrogen. In complexes 1-5 and 7, hydrogen bonds of type O-H center dot center dot center dot O and/or N-H center dot center dot center dot O are connecting the complex cations with the perchlorate anions/ligands to generate different dimensional supramolecular network structures, whereas in 6, the 3D network was formed through hydrogen bonding between the coordinated aqua and lattice water molecules. Non -covalent ring center dot center dot center dot ring interactions were also observed between pyridyl rings in complexes 1, 6 and 7, and between pyrazolyl rings as well as pyridyl ring in 2.

A novel series of polypyridyl adducts, [Sm(ntfa)3(NN)] (2–4), with ntfa = 4,4,4-trifluoro-1-(naphthalen-2-yl)-1,3-butanedionate, NN = 2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bipy), and 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2bipy) were synthesized from the precursor complex [Sm(ntfa)3(MeOH)2] (1) and the corresponding pyridyl ligands. Single X-ray crystallography showed that the complexes displayed 8-coordinated geometry. The solid pyridyl adducts 2–4 exhibited emission of luminescence in the NIR and visible regions with close quantum yields (QY = 0.20–0.25%). The magnetic data of 1–4 showed larger values than those expected for magnetically noncoupled Sm(III) complexes in the 6H5/2 ground state, with no saturation on the applied high magnetic field static at a temperature of 2 K.

Two dimensional classes of coordination polymers: 2D catena-[Cd(Me(3)en)(mu(1,5)-dca)(2)] (1) and catena-[Cd(ampip)(mu(1,1)-N-3)(mu(1,3)-N-3)(2)] (2) and 1D catena-[Cd(pren)(mu(1,1)-N-3)(2)] (3) and catena-[Cd(isq)(2)(mu(1,3)-NCS)(2)] (4) and catena-{[Cd-6(Me(3)pipz-H)(4)(Me(3)pipz)(2)(mu(1,3)-NCS)(12)][Cd(NCS)(6)]center dot 6H(2)O} (5), where Me(3)en = N,N,N'-trimethylethylenediamine, ampip = 1-(2-aminoethyl-piperidine, pren = N-(n-propyl)-ethylenediamine, isq = isoquinoline and Me(3)pipz = 1-(2-dimethylaminoethyl)-4-methylpiperazine, have been synthesized and structurally characterized. The degree of dimensionality and nuclearity were discussed in relation to the skeletal nature of the coligands and the bridging pseudohalides. The luminescence emission properties of the five complexes Cd(II) together with [Cd(TPA)(N-3)(2)]center dot H2O (6), [Cd-6(TPA)(4)(mu(1,1,3)-N-3)(4)(mu(1,1)-N-3)(6)](ClO4)(2)center dot 2H(2)O (7) and [Zn(TPA)(N3)2]center dot H2O (TPA = tris(2-methylpyridyl)amine) were investigated in methanol solution. No detectable or weak FL emission was observed in 1-5 complexes. The FL emission enhancement (lambda(ex) = 260 nm) in the visible region decreases in the order [Zn(TPA)(N-3)(2)]center dot H2O > [Cd(TPA)(N-3)(2)]center dot H2O (6) >= [Cd-6(TPA)(4)(mu(1,1,3)-N-3)4(mu(1,1)-N-3)(6)](ClO4)2 center dot 2H(2)O (7) with a red shift in the FL emission of the Cd(II)-TPA compounds.

Levofloxacin is a synthetic antibacterial agent that effectively inhibits DNA replication and is commonly used for the treatment of genitourinary, respiratory, and gastrointestinal tract infections. Metallodrugs interact with DNA, RNA, proteins, receptors, and lipids, making them unique and more effective as chemotherapy agents than their parent drugs. On this basis, herein four copper(II) complexes assembled from antibacterial levofloxacin ligand were synthesized and characterized using different analytical and spectroscopic measurements. X- ray perceived the formation of a ternary dimer and a ternary monomer complexes both in distorted square pyramidal geometry, with the existence of levofloxacin in a zwitterionic form. The other two complexes were verified, as binary and quaternary complexes having distorted octahedral geometry. Structure elucidation of these complexes was also explored by density functional theory methods and optimized geometrical parameters. Ternary dimer complex demonstrated higher stability than the ternary monomer complex. Natural bond orbital (NBO) analysis and molecular electrostatic potential (MESP)were investigated. Electronic absorption spectra of the optimized structure were performed using the time-dependent density functional theory (TD-DFT)/CAM-B3LYP method with LANL2DZ basis set in the gas phase. Binary copper complex exhibited significant antimicrobial activity and ternary monomer complex was more potent than ternary dimer complex. Interestingly levofloxacin and ternary copper complexes were completely devoid of antifungal activity, whereas octahedral binary and quaternary copper complexes displayed antifungal activity. In-silico molecular docking studies were accomplished with 3T88 (E-Coli) and 2GNP (S. pneumonia) receptors. Results proved powerful interaction at the docked site through the formation of hydrogen bond and van der wall interactions.

Four novel CeIII mononuclear complexes of formulas [Ce(ntfa)3(MeOH)2] (1), [Ce(ntfa)3(5,5'-Me2bipy)] (2), [Ce(ntfa)3(terpy)] (3), and [Ce(ntfa)3(bipy)2] (4), where ntfa = 4,4,4-trifluoro-1-(naphthalen-2-yl)butane-1,3-dionato, 5,5'-Me2bipy = 5,5'-dimethyl-2,2'-dipyridyl, terpy = 2,2':6',2″-terpyridine, and bipy = 2,2'-bipyridine, have been synthesized and structurally characterized with CeIII displaying coordination numbers of 8, 8, 9, and 10, respectively. Magnetic measurements indicate that all the complexes show a field-induced single-ion magnet behavior under a small applied dc field. The magnetic analysis shows the relevance of the different spin relaxation mechanisms in the magnetic relaxation of the CeIII compounds, with special emphasis on the local-mode process. Multiconfigurational calculations were also performed to get more information on the axiality of the compounds.

A series of heteroleptic copper(ii) complexes of the composition [Cu(L1-5)Cl]X, where X = ClO4 and/or PF6 and [bis(2-ethyl-di(3,5-dimethyl-1H-pyrazol-1-yl))-(6-methyl-(2-pyridylmethyl))]amine (L1), [bis(2-ethyl-di(3,5-dimethyl-1H-pyrazol-1-yl))-(3,4-dimethoxy-(2-pyridylmethyl))]amine (L2), [bis(2-ethyl-di(3,5-dimethyl-1H-pyrazol-1-yl)-(2-quinolymethyl)]amine (L3), [bis(2-ethyl-di(3,5-dimethyl-1H-pyrazolyl)-(di(3,5-dimethyl-1H-pyrazol-1-yl-methyl))]amine (L4) and [bis(2-ethyl-di(3,5-dimethyl-1H-pyrazol-1-yl)-(5-methyl-3-phenyl-1H-pyrazol-1-yl-methyl)]amine (L5), were prepared and thoroughly characterized including single-crystal X-ray diffraction technique. The in vitro cytotoxicity of complexes against A2780, A2780R, HOS and MCF-7 human cancer cell lines was evaluated using the MTT test. The results revealed that complexes [Cu(L1)Cl]PF6 (1-PF6), [Cu(L2)Cl]ClO4 (2-ClO4) and [Cu(L3)Cl]PF6 (3-PF6) are the most effective, with IC50 values ranging from 1.4 to 6.3 μM, thus exceeding the cytotoxic potential of metallodrug cisplatin (IC50 values ranging from 29.9 to 82.0 μM). The complexes [Cu(L4)Cl]PF6 (4-PF6) and [Cu(L5)Cl]PF6 (5-PF6) showed only moderate cytotoxicity against A2780, with IC50 = 53.6 μM, and 33.8 μM, respectively. The cell cycle profile, time-resolved cellular uptake, interactions with small sulfur-containing biomolecules (cysteine and glutathione), intracellular ROS production, induction of apoptosis and activation of caspases 3/7 were also evaluated in the case of the selected complexes. It has been found that the best performing complexes 1 and 2 cause cell arrest in the G2/M phase and induce apoptosis via the increase in production of ROS, dominantly due to the overproduction of superoxide.