Visible and NIR emitting Yb(iii) and Er(iii) complexes sensitized by β-diketonates and phenanthroline derivatives

Five new complexes namely, [Er(bta)₃(me-phen)] (1), [Yb(bta)₃(me-phen)] (2), [Gd(bta)3(me-phen)] (3), [Yb(bta)₃(pyz-phen)] (4), and [Er(tta)₃(pyz-phen)] (5) have been prepared with the fluorinated β-diketone ligands Hbta and Htta (Hbta = benzoyltrifluoroacetone and Htta = 2-thenoyltrifluoroacetone) combined with the azacyclo phenanthroline-derivatives, 5-methyl-1,10-phenanthroline (me-phen) and pyrazino[2,3-f][1,10]phenanthroline (pyz-phen). The crystal structures of 2, 4 and 5 have been solved by single-crystal X-ray diffraction. PXRD patterns show that 1–3 are isostructural. All the compounds exhibit a molecular structure with the metal atom in an eight-coordination geometry. The photophysical processes involved in the photoluminescence of the complexes are investigated; as a result, the radiative lifetimes (τ_Ln), the 4f–4f emission quantum efficiencies (Φ_Ln) and the energy-levels diagram are calculated.

Long lifetimes and high quantum yields are obtained in the reported complexes.     

A novel coordination mode of κ1-N-Br-pyridylbenz-(imida,oxa or othia)-zole to Pt(ii): synthesis,characterization, electrochemical and structural analysis

Herein, three novel Pt(ii) complexes with formula [trans-Pt(Br-PyBenz-X)(Cl)₂(DMSO)] (1–3) having Br-pyridylbenz-(imida, oxa or othia)-zole (L_1–3) derivatives as potential bidentate ligands, under an unusual κ¹-N-coordination mode are reported. All compounds were obtained straightforwardly via reaction of corresponding L_PB1–3 and [Pt(Cl)₂(DMSO)₂] (DMSO = dimethyl sulfoxide), at 100 °C in acetonitrile, respectively. 1–3 complexes were characterized by analytical and spectroscopic data: melting point, FT-IR, Raman, UV/Vis and NMR experiments. Cyclic voltammetry studies show an irreversible two-electron process at −0.50 and −0.51 V, which was ascribed to the Pt(ii)/Pt(iv) couple, for complexes 2 and 3. The crystal structure of complex 2 was elucidated by single-crystal X-ray diffraction, where the platinum atom exhibits a square plane geometry, where L_PB2 adopts an unusual mono-coordinated mode via an N-κ¹-benzoxazole ring. According to DFT calculations the first N-coordination exchanging one DMSO molecule is favourable, while the second N-coordination is highly impeded.

Three novel platinum(ii) complexes with the general formula [trans-Pt(Br-PyBenz-X)(Cl)₂(DMSO)] containing Br-pyridylbenz(imida, oxa or othia)zole derivatives, under an unusual N-κ¹-coordination mode were synthesized.     

Heteroleptic Re(CO)2+ and Re(CO)3+ complexes with α-diimines: similarities and differences in their luminescence properties

The photophysical properties of two series of phosphorescent rhenium(i) complexes, [Re(CO)₂(N^N)(tpp)₂]⁺ and [Re(CO)₃(N^N)(tpp)]⁺ with carbon monoxide (CO), triphenylphosphine (tpp) and α-diimine (N^N) ligands have been investigated in deoxygenated acetonitrile solution at room temperature and in solid methanol/ethanol 1 : 1 matrices at 77 K. The complexes display moderate to strong phosphorescence which is related to the N^N ligand modulated metal-to-ligand charge-transfer S₀ ← ³*MLCT or intraligand S₀ ← ³*LC transitions. Luminescence properties of the investigated series have been found to be very similar but some intrinsic differences between them are clearly seen. Whereas the [Re(CO)₂(N^N)(tpp)₂]⁺ series shows MLCT emission in both temperature regimes studied, the [Re(CO)₃(N^N)(tpp)]⁺ series exhibits intrinsic changes in its emission character when the measurement temperature is lowered from 298 to 77 K. In both investigated series, their emission characteristics are strongly affected by the nature of coordinated α-diimine N^N ligands. The observed trends, changes in the radiative k_r and non-radiative k_nr deactivation rate constants, have been compared with those found for the previously investigated [Re(CO)₃(N^N)(Cl)], [Re(CO)₃(N^N)(CH₃CN)]⁺, and [Re(CO)₂(N^N)(dppv)]⁺ series (dppv = cis-1,2-bis(diphenylphosphino)-ethene). Similarities and differences in the spectroscopic and photophysical properties of five series of the Re(CO)₃⁺ and Re(CO)₂⁺ complexes have been analyzed in the view of results from DFT and TD-DFT computation and the emission band-shape analyses performed according to the Marcus–Jortner formalism.

We report results from comparative studies of luminescence properties of five series of α-diimine rhenium(i) complexes.     

Synthesizing and evaluating the photodynamic efficacy of asymmetric heteroleptic A7B type novel lanthanide bis-phthalocyanine complexes

In this study heteroleptic A₇B type novel Lu(iii) and Eu(iii) lanthanide phthalocyanines (LnPc(Pox)[Pc′(AB₃SH)]) with high extinction coefficients have been synthesized as candidate photosensitizers with reaction yields higher than 33%. The singlet oxygen quantum yields of LuPc(Pox)[Pc′(AB₃SH)] and EuPc(Pox)[Pc′(AB₃SH)], respectively, were measured 17% and 1.4% by the direct method in THF. The singlet oxygen quantum yield of LuPc(Pox)[Pc′(AB₃SH)] in THF is the highest among lutetium(iii) bis-phthalocyanine complexes to date. The photodynamic efficacy of the heteroleptic lanthanide phthalocyanines was evaluated by measuring cell viabilities of A549 and BEAS-2B lung cells, selected to representing in vitro models for testing cancer and normal cells against potential drugs. The cell viabilities demonstrated concentration dependent behavior and were varied by the type of phthalocyanines complexes. Irradiation of the cells for 30 minutes with LED array at 660 nm producing flux of 0.036 J cm⁻² s⁻¹ increased cell death for LuPcPox-OAc, LuPc(Pox)[Pc′(AB₃SH)] and ZnPc. The IC₅₀ concentrations of LuPc(Pox)[Pc′(AB₃SH)] and ZnPc were determined to be below 10 nM for both cell lines, agreeing very well with the singlet oxygen quantum yield measurements. These findings suggest that LuPc(Pox)[Pc′(AB₃SH)] and particularly LuPcPox-OAc are promising drug candidates enabling lowered dose and shorter irradiation time for photodynamic therapy.

Novel bis-lanthanide Lu(iii) and Eu(iii) phthalocyanine complexes have been designed/synthesized and tested their photodynamic efficacy for A549 and BEAS-2B cells in vitro conditions as candidate photosensitizers in PDT.     

Synthesis,structures and properties of six lanthanide complexes based on a 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline ligand

Six lanthanide complexes [Tb(2-NCP)₂(NO₃)]_n (1), [Eu(2-NCP)₂(3-PYC)]_n (2), [Sm(2-NCP)₂(3-PYC)]_n (3), [Eu(2-NCP)(SA)]_n (4), [Tb(2-NCP)(SA)]_n (5) and [Tb(2-NCP)(AA)]_n (6) (2-HNCP = 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline, 3-HPYC = pyridine-3-carboxylic acid, H₂SA = succinic acid, H₂AA = adipic acid) have been synthesized by hydrothermal route, and the crystal structures were analyzed through elemental analysis, infrared spectroscopy, single crystal X-ray diffraction. Complexes 1 and 6 present two-dimensional (2D) layers, which are further connected to three-dimensional (3D) supramolecular architectures through C–H⋯π interactions. Complexes 2 and 3 exhibit infinite one-dimensional chains. Finally, the neighboring chains are packed by C–H⋯π interactions, giving rise to 3D supramolecular network. Complexes 4 and 5 display 2D layers, which are further extend to 3D supramolecular structures via C–H⋯O intermolecular hydrogen bonding. Six complexes possess good thermal stabilities, characteristic photoluminescence properties, and photocatalytic activities for the degradation of organic dyes under visible light irradiation. In addition, the complex 6 exhibits significantly enhanced photocatalytic activity for methylene blue, and the degradation rate could reach 81.2% in 370 min. Meanwhile trapping experiments indicated that the hole, ·O₂⁻ and ·OH are the main activated species. Furthermore, by comparing the photoluminescent and photocatalytic mutation results of same metal complexes induced by interconversion of coligands, we confirm that the properties mutation induced by coligands is much obvious and controllable.

Six lanthanide complexes based on 2-HNCP possess good thermal stabilities, characteristic photoluminescence properties, and photocatalytic activities for organic dyes degradation under visible light irradiation.     

Four rare structurally characterized hetero-pentanuclear [Zn4Ln] bis(salamo)-type complexes: syntheses,crystal structures and spectroscopic properties

Four new hetero-pentanuclear 3d–4f complexes [Zn₄(L)₂La(NO₃)₂(OEt)(H₂O)] (1), [Zn₄(L)₂Ce(NO₃)₂(OMe)(MeOH)] (2), [Zn₄(L)₂Pr(NO₃)₂(OEt)(EtOH)] (3) and [Zn₄(L)₂Nd(NO₃)₂(OMe)(MeOH)] (4) were synthesized by the reactions of a newly synthesized octadentate bis(salamo)-based tetraoxime ligand (H₄L) with Zn(OAc)₂·2H₂O and Ln(NO₃)₃·6H₂O (Ln = La, Ce, Pr and Nd), respectively, and characterized via elemental analyses, FT-IR, UV-Vis spectroscopy and single crystal X-ray crystallography. The X-ray crystallographic investigation revealed that all Zn^II ions were located in N₂O₃ coordination spheres, and possessed a trigonal bipyramid coordination environment. The Ln^III ion lay in an O₈ coordination sphere, and adopted a distorted square antiprismatic coordination environment. Furthermore, supramolecular interactions and fluorescence properties were investigated.

Four new hetero-pentanuclear 3d–4f complexes 1–4 were synthesized and characterized. Supramolecular interactions and fluorescence properties of complexes 1–4 were investigated.     

Synthesis,characterization and biological evaluation of dipicolylamine sulfonamide derivatized platinum complexes as potential anticancer agents

Three new Pt complexes, [PtCl₂(N(SO₂(2-nap))dpa)], [PtCl₂(N(SO₂(1-nap))dpa)] and [PtCl₂(N(SO₂pip)dpa)], containing a rare 8-membered ring were synthesized in good yield and high purity by utilizing the ligands N(SO₂(2-nap))dpa, N(SO₂(1-nap))dpa and N(SO₂pip)dpa, which contain a dipicolylamine moiety. Structural studies of all three complexes confirmed that the ligands are bound in a bidentate mode via Pt–N_(pyridyl) bonds forming a rare 8-membered ring. The intense fluorescence displayed by the ligands is quenched upon coordination to Pt. According to time dependent density functional theory (TDDFT) calculations, the key excitations of N(SO₂(2-nap))dpa and [PtCl₂(N(SO₂(1-nap))dpa)] involve the 2-nap-ligand-centered π → π* excitations. While all six compounds have shown antiproliferative activity against human breast cancer cells (MCF-7), the N(SO₂pip)dpa and N(SO₂(2-nap))dpa ligands and [PtCl₂((NSO₂pip)dpa)] complex have shown significantly high cytotoxicity, directing them to be further investigated as potential anti-cancer drug leads.

Three new Pt complexes, [PtCl₂(N(SO₂(2-nap))dpa)], [PtCl₂(N(SO₂(1-nap))dpa)] and [PtCl₂(N(SO₂pip)dpa)], containing a rare 8-membered ring were synthesized in good yield and high purity by utilizing ligands which contain a dipicolylamine moiety.     

Density functional theory investigation on iridium(iii) complexes for efficient blue electrophosphorescence

The geometrical structures, electronic structures, optoelectronic properties and phosphorescence efficiencies of four blue-emitting phosphors [Ir(fpmi)₂(pyim)] (1), [Ir(pyim)₂(fpmi)] (2), [Ir(fpmi)₂(fptz)] (3), [Ir(tfmppz)₂(pyim)] (4), [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C,C²′; pyim = 2-(1H-imidazol-2-yl)pyridinato; fptz = 5-(trifluoromethyl-2H-1,2,4-triazol-3-yl)pyridine; tfmppz = 1-(4-trifluoromethylphenyl)pyrazolyl] were investigated by DFT and TDDFT methods. We first optimized geometrical structures in the ground and lowest triplet states, and computed the absorption and emission spectra of 1 and 5[Ir(fpmi)₂(pypz)] [pypz = 2-(1H-pyrazol-5-yl)pyridinato], which have been synthesized and characterized in a laboratory, using three functionals, B3LYP, CAM-B3LYP, and M062X. The calculation results were compared with relevant experimental data to assess the performance of the functionals. The suitable methods and functionals were then applied to study properties of the three other complexes. The HOMOs of 1–3 are composed of d(Ir) and π(cyclometalated ligands), however, the HOMO of 4 resides on the pyim ligand, while the LUMOs of all four complexes are dominantly localized on the chelating ligands. The calculated absorption results show that the corresponding absorption peaks for the four mainly studied complexes are almost at the same positions, however, the absorption intensities of the bands differ largely from each other. The lowest energy emissions of the four complexes are localized at 507, 512, 468, and 513 nm, respectively. In order to estimate their efficiencies, we carried out simplified radiative rate constant calculations. It turns out that complex 3, which possesses the shortest emission wavelength and the largest radiative rate constant (k_r) value, can be considered as a highly efficient blue-emitting iridium(iii) complex.

The geometrical structures, electronic structures, optoelectronic properties and phosphorescence efficiencies of blue-emitting phosphors [Ir(fpmi)₂(pyim)], [Ir(pyim)₂(fpmi)], [Ir(fpmi)₂(fptz)], [Ir(fpmi)₂(pypz)] and [Ir(tfmppz)₂(pyim)]), were investigated by DFT and TDDFT methods.     

Microwave-assisted synthesis of ruthenium(ii) complexes containing levofloxacin-induced G2/M phase arrest by triggering DNA damage

Ru(ii) complexes have attracted increasing attention as promising antitumor agents for their relatively low toxicity, high affinity to DNA molecules, and correlation with multiple targets. Meanwhile, quinolones are synthetic antibacterial agents widely used in the clinical practice. In this paper, two novel Ru(ii) complexes coordinated by levofloxacin (LOFLX), [Ru(bpy)₂(LOFLX)]·2ClO₄ (1), and [Ru(dmbpy)₂(LOFLX)]·2ClO₄ (2) (bpy = 2,2′-bipyridine, dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized with high efficiency under microwave irradiation and characterized by ESI-MS, ¹H NMR, and ¹³C NMR. The binding behavior of these complexes with double-strand calf thymus DNA(CT-DNA) was investigated using spectroscopy, molecular docking, and density functional theory calculations. Results showed that 2 exhibited higher binding affinity than 1 and LOFLX. Further studies showed that 2 could induce the G2/M phase arrest of A549 cells via DNA damage. In summary, these results indicated that 2 could be developed as a potential anticancer agent in treatment of lung cancer through the induction of cell cycle arrest at G2/M phase by triggering DNA damage.

This study showed that levofloxacin-based ruthenium(ii) complex 2 effectively inhibited the growth of A549 cells by inducing G2/M phase arrest through triggering DNA damage.     

Two bis-ligand-coordinated Zn(ii)-MOFs for luminescent sensing of ions,antibiotics and pesticides in aqueous solutions

Two organometallic complexes with two and three-dimensional architectures were constructed by using multiple ligands and Zn(ii) ions: [Zn₃(BTC)₂(DTP)₄(H₂O)₂]·(H₂O)₄ (Zn-1) (BTC = benzene-1,3,5-tricarboxylic acid and DTP = 3,5-di(1,2,4-triazol-1-yl)pyridine) and [Zn₂(NTD)₂(DTP)] (Zn-2) (NTD = 1,4-naphthalenedicarboxylic acid). The as-prepared complexes were characterized by single-crystal X-ray diffraction (SCXRD), elemental analysis, powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and fluorescence analysis. Fluorescence sensing tests revealed that the two complexes are effective, sensitive and selective toward cationic Fe³⁺ and anionic MnO₄⁻ and Cr₂O₇²⁻. During the antibiotic sensing process, cefixime (CFX) for Zn-1 and nitrofurantoin (NFT) for Zn-2 exhibited the highest quenching efficiencies. For sensing pesticides, the highest quenching efficiencies were exhibited by imidacloprid (IMI) toward Zn-1 and Zn-2. The fluorescence quenching of the complexes that was induced by antibiotics, pesticides and MnO₄⁻ was attributed to both the inner filter effect (IFE) and the fluorescence resonance energy transfer (FRET) effect.

The fluorescence and pollutant sensing of two Zn-complexes was investigated, and the corresponding mechanism was proposed.     

Thermally activated delayed fluorescence in luminescent cationic copper(i) complexes

In this work, the photophysical characteristics of [Cu(N^N)₂]⁺ and [Cu(N^N)(P^P)]⁺ complexes were described. The concept of thermally activated delayed fluorescence (TADF) and its development throughout the years was also explained. The importance of ΔE_(S1–T1) and spin-orbital coupling (SOC) values on the TADF behavior of [Cu(N^N)₂]⁺ and [Cu(N^N)(P^P)]⁺ complexes is discussed. Examples of ΔE_(S1–T1) values reported in the literature were collected and some trends were proposed (e.g. the effect of the substituents at the 2,9 positions of the phenanthroline ligand). Besides, the techniques (or calculation methods) used for determining ΔE_(S1–T1) values were described. The effect of SOC in TADF was also discussed, and examples of the determination of SOC values by DFT and TD-DFT calculations are provided. The last chapter covers the applications of [Cu(N^N)₂]⁺ and [Cu(N^N)(P^P)]⁺ TADF complexes and the challenges that are still needed to be addressed to ensure the industrial applications of these compounds.

Bibliographic review of cationic Cu(i) complexes that undergo Thermally Activated Delayed Fluorescence (TADF). From the first findings found in the homoleptic and heteroleptic Cu(i)-TADF complexes to the use of this property in lighting devices.     

A new synthetic route for the preparation of [Os3(CO)10(μ-OH)(μ-H)] and its reaction with bis(diphenylphosphino)methane (dppm): syntheses and X-ray structures of two isomers of [Os3(CO)8(μ-OH)(μ-H)(μ-dppm)] and [Os3(CO)7(μ3-CO)(μ3-O)(μ-dppm)]

The triosmium cluster [Os₃(CO)₁₀(μ-OH)(μ-H)] containing bridging hydride and hydroxyl groups at a common Os–Os edge was obtained in good yield (ca. 75%) from the hydrolysis of the labile triosmium cluster [Os₃(CO)₁₀(NCMe)₂] in THF at 67 °C. [Os₃(CO)₁₀(μ-OH)(μ-H)] reacts with dppm at 68 °C to afford the isomeric clusters 1 and 2 with the general formula [Os₃(CO)₈(μ-OH)(μ-H)(μ-dppm)] that differ by the disposition of bridging dppm ligand. Cluster 1 is produced exclusively from the reaction of [Os₃(CO)₁₀(μ-OH)(μ-H)] with dppm in CH₂Cl₂ at room temperature in the presence of added Me₃NO. Heating cluster 1 at 81 °C furnishes 2 in a process that likely proceeds by the release of one arm of the dppm ligand, followed by ligand reorganization about the cluster polyhedron and ring closure of the pendent dppm ligand. The oxo-capped [Os₃(CO)₇(μ₃-CO)(μ₃-O)(μ-dppm)] (3) has been isolated starting from the thermolysis of either 1 or 2 at 139 °C. Reactions of [Os₃(CO)₁₀(μ-dppm)] with ROH (R = Me, Et) in the presence of Me₃NO at 80 °C furnish [Os₃(CO)₈(μ-OH)(μ,η¹,κ¹-OCOR)(μ-dppm)] (4, R = Me; 5, R = Et). Clusters 1–5 have been characterized by a combination of analytical and spectroscopic studies, and the molecular structure of each product has been established by X-ray crystallography. The bonding in these products has been examined by electronic structure calculations, and cluster 1 is confirmed as the kinetic product of substitution, while cluster 2 represents the thermodynamically favored isomer.

The cluster [Os₃(CO)₁₀(μ-OH)(μ-H)] was obtained in 75% from the hydrolysis of [Os₃(CO)₁₀(NCMe)₂].     

Novel tetrahedral cobalt(ii) silanethiolates: structures and magnetism

Three heteroleptic complexes of Co(ii) tri-tert-butoxysilanethiolates have been synthesized with piperidine [Co{SSi(OtBu)₃}₂(ppd)₂] 1, piperazine [Co{SSi(OtBu)₃}₂(NH₃)]₂(μ-ppz)·2CH₃CN 2, and N-ethylimidazole [Co{SSi(OtBu)₃}₂(etim)₂] 3. The complexes have been characterized by a single-crystal X-ray, revealing their tetrahedral geometry on Co(ii) coordinated by two nitrogen and two sulfur atoms. Complexes 1 and 3 are mononuclear, whereas 2 is binuclear. The spectral properties and thermal properties of 1–3 complexes were established by FTIR spectroscopy for solid samples and TGA. The magnetic properties of complexes 1, 2, and 3 have been investigated by static magnetic measurements and X-band EPR spectroscopy. These studies have shown that 1 and 3, regardless of the similarity in structure of CoN₂S₂ cores, demonstrate different types of local magnetic anisotropy. Magnetic investigations of 2 reveal the presence of weak antiferromagnetic intra-molecular Co(ii)–Co(ii) interactions that are strongly influenced by the local magnetic anisotropy of individual Co(ii) ions.

Structural, spectral and thermal properties of three tetrahedral Co(ii) silanethiolates were established by XRD, FTIR for solid samples and TGA. The magnetic properties were investigated by static magnetic measurements and X-band EPR spectroscopy.     

Synthesis,characterization, and photoluminescent studies of three-coordinate Cu(i)–NHC complexes bearing unsymmetrically-substituted dipyridylamine ligands

A series of heteroleptic three-coordinate Cu(i) complexes bearing monodentate N-heterocyclic carbene (NHC) ligands of the type 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), and bidentate N-donor ligands of the type unsymmetrically-substituted dimethyl dipyridylamine (Me₂Hdpa) and bis(mesityl)biazanaphthenequinone (mesBIAN) have been synthesized. The complexes [Cu(IPr)(3,4′-Me₂Hdpa)]PF₆, 1; [Cu(IPr)(3,5′-Me₂Hdpa)]PF₆, 2; [Cu(IPr)(3,6′-Me₂Hdpa)]PF₆, 3; [Cu(IPr)(mesBIAN)]PF₆, 6; [Cu(SIPr)(3,4′-Me₂Hdpa)]PF₆, 7; [Cu(SIPr)(3,5′-Me₂Hdpa)]PF₆, 8; and [Cu(SIPr)(3,3′-Me₂Hdpa)]PF₆, 11 have been characterized by ¹H and ¹³C NMR spectroscopies, elemental analysis, cyclic voltammetry, and photophysical studies in solid and solution phase. Single crystal X-ray structures were obtained for all complexes except 11. The crystallographic data reveal a mononuclear structure for all complexes with the copper atom ligated by one C and two N atoms. The UV-Vis absorption spectra of all dipyridylamine complexes in CH₂Cl₂ show a strong ligand-centered absorption band around 250 nm and a strong metal-to-ligand charge transfer (MLCT) band around 300 nm. When irradiated with UV light, the complexes exhibit strong emission maxima at 453–482 nm with photoluminescence quantum yields (PLQY) ranging from 0.21 to 0.87 in solid state. While the PLQY values are comparable to those of the symmetrical [Cu(IPr)(Me₂Hdpa)]PF₆ complexes, a stabilizing CH–π interaction has been reduced in the current systems. In particular, complex 3 lacks any strong CH–π interaction, but emits more efficiently than 1 and 2 wherein the interactions exist. Structural data analysis was performed to clarify the role of ligands'' plane angle and the NH/CH⋯F interactions to the observed light interaction of unsymmetrical [Cu(NHC)(Me₂Hdpa)]PF₆ complexes. DFT calculations were performed to assist in the assignment of the electronic structure and excited state behavior of the complexes.

The photoluminescent Cu(i)–NHC complexes bearing unsymmetrical dipyridylamine ligands have been synthesized and characterized. The structure–light reactivity has been elucidated.     

From cyclic amines and acetonitrile to amidine zinc(ii) complexes

A seemingly simple combination of [Zn(quin)₂(H₂O)] (quin⁻ = quinaldinate) and a selected secondary cyclic amine, piperidine (pipe), pyrrolidine (pyro) or morpholine (morph), afforded in acetonitrile a number of products: anionic homoleptic quinaldinate, neutral heteroleptic quinaldinate/amine and quinaldinate/amidine complexes. The piperidine and pyrrolidine systems underwent reaction with acetonitrile to give amidines. The in situ formed piperidinoacetamidine (pipeam) or pyrrolidinoacetamidine (pyroam) coordinated to zinc(ii). Reactions with piperidine led to trans-[Zn(quin)₂(pipe)₂]·2CH₃CN (1), [Zn(quin)₂(pipe)]·cis-[Zn(quin)₂(pipe)₂] (2), pipeH[Zn(quin)₃]·CH₃CN (3), [Zn(quin)₂(pipeam)]·CH₃CN (4a), [Zn(quin)₂(pipeam)]·2CHCl₃ (4b), pipeamH[Zn(quin)₃] (5) and pipeamH[Zn(quin)₂(CH₃COO)]·acetamide (6) (pipeH⁺ and pipeamH⁺ denote protonated amine or amidine). By analogy, [Zn(quin)₂(pyro)₂] (7), pyroH[Zn(quin)₃]·CH₃CN (8), pyroH[Zn(quin)₂Cl] (9), [Zn(quin)₂(pyroam)]·CH₃CN·0.5pyroam·0.5H₂O (10a), [Zn(quin)₂(pyroam)]·2CHCl₃ (10b), [Zn(quin)₂(pyroam)]·CH₂Cl₂ (10c) and pyroamH[Zn(quin)₃] (11) were obtained in the pyrrolidine reactions. The morpholine system allowed isolation of only two novel products, trans-[Zn(quin)₂(morph)₂] (12) and morphH[Zn(quin)₃]·CH₃CN (13). Importantly, no amidine could be isolated. Instead, in autoclaves at 105 °C morpholine degraded to ammonia, as confirmed by mass spectrometry of the gas phase. pyroamH[Zn(quin)₃] exists in two polymorphs which differ in the binding modes of quinaldinate ligands. In 11triclinic, the metal ion of [Zn(quin)₃]⁻ features a five-coordinate environment, whereas that in 11monoclinic is surrounded by six donors. Stabilities of the [Zn(quin)₃]⁻ isomers were assessed with DFT calculations. The one with a six-coordinate zinc(ii) ion was found to be more stable than its five-coordinate counterpart. Favorable intermolecular interactions in the solid state stabilize both and reduce the energy difference between them. The calculations show the conversion of the five-coordinate [Zn(quin)₃]⁻ into its coordinatively saturated isomer to be an almost barrierless process.

Piperidine and pyrrolidine, both belonging to a group of secondary cyclic amines, reacted with acetonitrile in the presence of zinc(ii) to give the corresponding amidines that coordinated to the metal through their imine nitrogen.     

Reactions of triosmium and triruthenium clusters with 2-ethynylpyridine: new modes for alkyne C–C bond coupling and C–H bond activation

The reaction of the trimetallic clusters [H₂Os₃(CO)₁₀] and [Ru₃(CO)₁₀L₂] (L = CO, MeCN) with 2-ethynylpyridine has been investigated. Treatment of [H₂Os₃(CO)₁₀] with excess 2-ethynylpyridine affords [HOs₃(CO)₁₀(μ-C₅H₄NCH=CH)] (1), [HOs₃(CO)₉(μ₃-C₅H₄NC CH₂)] (2), [HOs₃(CO)₉(μ₃-C₅H₄NC CCO₂)] (3), and [HOs₃(CO)₁₀(μ-CH CHC₅H₄N)] (4) formed through either the direct addition of the Os–H bond across the C C bond or acetylenic C–H bond activation of the 2-ethynylpyridine substrate. In contrast, the dominant pathway for the reaction between [Ru₃(CO)₁₂] and 2-ethynylpyridine is C–C bond coupling of the alkyne moiety to furnish the triruthenium clusters [Ru₃(CO)₇(μ-CO){μ₃-C₅H₄NC CHC(C₅H₄N) CH}] (5) and [Ru₃(CO)₇(μ-CO){μ₃-C₅H₄NCCHC(C₅H₄N)CHCHC(C₅H₄N)}] (6). Cluster 5 contains a metalated 2-pyridyl-substituted diene while 6 exhibits a metalated 2-pyridyl-substituted triene moiety. The functionalized pyridyl ligands in 5 and 6 derive via the formal C–C bond coupling of two and three 2-ethynylpyridine molecules, respectively, and 5 and 6 provide evidence for facile alkyne insertion at ruthenium clusters. The solid-state structures of 1–3, 5, and 6 have been determined by single-crystal X-ray diffraction analyses, and the bonding in the product clusters has been investigated by DFT. In the case of 1, the computational results reveal a rare thermodynamic preference for a terminal hydride ligand as opposed to a hydride-bridged Os–Os bond (3c,2e Os–Os–H bond).

The reactivity of 2-ethynylpyridine at low-valent triosmium and triruthenium centers has been investigated.     

Silver(i) pyridylphosphonates – synthesis,structure, stability and light-insensitivity investigation

Two silver(i) complexes, {[Ag₇(2-pypo)₃(NO₃)]}_n (1) and [Ag(3-pypoH)(3-pypoH₂)] (2) (pypoH₂ – pyridylphosphonic acid) were prepared and characterized by relevant methods in the solid state (elemental, spectral, thermal and structural analysis). Typical argentophilic interactions were observed in complex 1. The synthesized Ag(i) complexes were tested toward reduction to silver(0) using short wavelength UV-radiation and they revealed remarkable light-insensitivity in comparison to silver nitrate. SEM experiments were performed to observe the reduction of silver after the UV-light exposure of the samples. Light-insensitivity with the examined thermal stability and insolubility of the new complexes demonstrates their high potential to be used as light-insensitive materials in medical devices.

Two silver(i) complexes, {[Ag₇(2-pypo)₃(NO₃)]}_n (1) and [Ag(3-pypoH)(3-pypoH₂)] (2) (pypoH₂ – pyridylphosphonic acid) were prepared and characterized by relevant methods in the solid state and were tested toward reduction to silver(0).     

Ru(ii)–N-heterocyclic carbene complexes: synthesis,characterization, transfer hydrogenation reactions and biological determination

A series of ruthenium(ii) complexes with N-heterocyclic carbene ligands were successfully synthesized by transmetalation reactions between silver(i) N-heterocyclic carbene complexes and [RuCl₂(p-cymene)]₂ in dichloromethane under Ar conditions. All new compounds were characterized by spectroscopic and analytical methods. These ruthenium(ii)–NHC complexes were found to be efficient precatalysts for the transfer hydrogenation of ketones by using 2-propanol as the hydrogen source in the presence of KOH as a co-catalyst. The antibacterial activity of ruthenium N-heterocyclic carbene complexes 3a–f was measured by disc diffusion method against Gram positive and Gram-negative bacteria. Compounds 3d exhibited potential antibacterial activity against five bacterial species among the six used as indicator cells. The product 3e inhibits the growth of all the six tested microorganisms. Moreover, the antioxidant activity determination of these complexes 3a–f, using 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azinobis-3-ethylbenzothiazoline-6-sulphonic acid (ABTS) as reagent, showed that compounds 3b and 3d possess DPPH and ABTS antiradical activities. From a concentration of 1 mg ml⁻¹, these two complexes presented a similar scavenging activity to that of the two used controls gallic acid (GA) and butylated hydroxytoluene (BHT). From a concentration of 10 mg ml⁻¹, the percentage inhibition of complexes 3b and 3d was respectively 70% and 90%. In addition, these two Ru–NHC complexes exhibited antifungal activity against Candida albicans. Investigation of the anti-acetylcholinesterase activity of the studied complexes showed that compounds 3a, 3b, 3d and 3e exhibited good activity at 100 μg ml⁻¹ and product 3d is the most active. In a cytotoxicity study the complexes 3 were evaluated against two human cancer cell lines MDA-MB-231 and MCF-7. Both 3d and 3e complexes were found to be active against the tested cell lines showing comparable activity with examples in the literature.

A series of ruthenium(ii) complexes with N-heterocyclic carbene ligands were successfully synthesized by transmetalation reactions between silver(i) N-heterocyclic carbene complexes and [RuCl₂(p-cymene)]₂ in dichloromethane under Ar conditions.