Cytotoxic effect,generation of reactive oxygen/nitrogen species and electrochemical properties of Cu(ii) complexes in comparison to half-sandwich complexes of Ru(ii) with aminochromone derivatives

This paper describes the synthesis of new 6-aminoflavone (6AFl (3)) and 6-aminochromone (6AC (4)) complexes with Cu(ii) and Ru(ii) ions ([Cu(6AC)₂Cl₂] (3a), [Cu(6AFl)₂Cl₂] (4a), [Ru(p-cymene)(6AC)Cl₂] (4b)) and comparison of their properties with the previously described 7-aminoflavone (7AFl (1)) and 7-amino-2-methylchromone (7A2MC (2)) analogues. The cytotoxic effect of all these complexes against two human leukaemia cell lines (HL-60 and NALM-6), melanoma WM-115 cells and COLO205 cells, is determined. The cytotoxicity of copper(ii) complexes, especially [Cu(6AFl)₂Cl₂] (3a) was higher than ruthenium(ii) complexes with the same ligands. Their cytotoxic potency was also stronger in comparison to the referential agents like cisplatin. The pro-oxidative properties were determined for the most active complexes and their ability to generate ROS (reactive oxygen species)/RNS (reactive nitrogen species) in cancer cells was confirmed. The type of ligand and the chemical structure of the tested complexes had an influence on the level of ROS/RNS generated in cancer cells. The redox properties of the copper complex compounds were evaluated by cyclic voltammetry, and compared with the data for Ru(ii) complexes. The reduction and oxidation processes of Ru(iii)/Ru(ii) and Cu(ii)/Cu(i) were described as quasi-reversible.

New Cu(ii)/Ru(ii) complexes with 6-aminoflavone/chromone derivatives as ligands were synthesized and characterized. Their cytotoxicity, pro-oxidative and redox properties were investigated.     

A stable Ln(iii)-functionalized Cd(ii)-based metal–organic framework: tunable white-light emission and fluorescent probe for monitoring bilirubin

A novel anionic Cd(ii)-based metal–organic framework, H₂[Cd₉(DDB)₄(BPP)₄(H₂O)₁₄]·4H₂O·2DMA (1), was successfully obtained with a rigid carboxylate ligand 3,5-di(2′,4′-dicarboxylphenyl)benzoic acid (H₅DDB) and a flexible pyridyl ligand 1,3-bis(4-pyridyl)propane (BPP). Complex 1 contains two-dimensional (2D) honeycomb structures and one-dimensional (1D) chain structures. The adjacent 2D structures are linked by strong intermolecular hydrogen bonds to form an ABAB 3D supramolecular structure, where the 1D chain structures traverse the channels of the 2D structures. Due to the anionic framework, Ln(iii) ions (Ln = Eu and Tb) can be encapsulated in the framework of 1 by a post-synthetic modification process to obtain Ln(iii)@1, where 1.09Eu(iii)@1 (1a) and 0.658Tb(iii)@1 (1b) can be obtained by soaking complex 1 in a Eu(NO₃)₃·6H₂O or Tb(NO₃)₃·6H₂O aqueous solution for 48 h. The liquid-state emission spectra of Ln(iii)@1 can be tuned to be a white light emission by changing the Eu(iii)/Tb(iii) molar ratio in solution. Moreover, 1b can be used as a “turn-off” fluorescent probe for bilirubin with a low detection limit of 0.250 μM in phosphate buffer solution (pH = 7.4), which presents excellent sensitivity, high selectivity, and reusability. Furthermore, the devised fluorescent probe in serum also exhibits the fluorescence “turn-off” process with a low detection limit of 0.279 μM, and the recovery rate of bilirubin is 99.20–101.9%. The possible mechanisms of the fluorescence “turn-off” process can be explained by resonance energy transfer, and the weak interaction between 1b and bilirubin.

A novel anionic Cd(ii)-based metal–organic framework was used toencapsulateLn(iii) ions, which exhibits tunable luminescence and selective sensing of bilirubin.     

Extraction of Pd(ii) and Pt(ii) from aqueous hydrochloric acid with 1,3-diaminocalix[4]arene: switching of the extraction selectivity by using different extraction modes

The extraction ability of 1,3-diaminocalix[4]arene (2: H₂L) toward platinum group metals (PGMs) has been investigated, which revealed that 2 is able to extract Pd(ii) and Pt(ii) from hydrochloric acid via different extraction modes. The extraction species for Pd(ii) and Pt(ii) are [PdL] and [Pt₂Cl₆(H₃L)₂], respectively, as evidenced by equilibrium analysis and X-ray crystallography. In [PdL], the two phenoxide oxygens and two amino nitrogens of L²⁻ coordinate to the Pd ion. On the other hand, in [Pt₂Cl₆(H₃L)₂], two anionic trichloro complexes PtCl₃⁻ are sandwiched between two H₃L⁺, in which one amino nitrogen directly coordinates to a PtCl₃⁻ species and another protonated amino group forms an ion pair with another PtCl₃⁻. Utilizing the different extraction modes, switching of the extraction selectivity has been achieved in the competitive extraction between Pd(ii) and Pt(ii) by varying the concentrations of H⁺ and Cl⁻ in the aqueous phase. Finally, from the extracted organic phase, back-extraction of Pd(ii) and Pt(ii) was easily performed, respectively.

1,3-Diaminocalix[4]arene shows extraction ability toward Pd(ii) and Pt(ii), the selectivity of which can be switched by changing the concentrations of H⁺ and Cl⁻ in the aqueous phase.     

Cu(ii)/Ni(ii)–organic frameworks constructed from the homometallic clusters by 5-(2-carboxyphenoxy)isophthalic acid and N-ligand: synthesis,structures and visible light-driven photocatalytic properties

Four new complexes, namely, Cu₂(O-cpia)(btb)_0.5·(OH) (1), Cu₃(O-cpia)₂(bpy)₂ (2), [Ni₂(O-cpia)(phen)·(OH)·H₂O]·2H₂O (3) and [Ni₃(O-cpia)₂(bpy)₃·2H₂O]·2H₂O (4) (O-cpia = 5-(2-carboxyphenoxy)isophthalic acid, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bpy = 4,4′-bipyridine) were successfully isolated under hydrothermal conditions. The four complexes exhibit different architectures constructed from different homometallic clusters varying from mononuclear, binuclear to tetranuclear metal(ii) polyhedra as Second Building Blocks (SBUs). 1 features a 3D framework constructed from the tetranuclear clusters [Cu₄(μ₃-OH)₂] as SBUs, linked with Cu(1)O₄N and Cu(2)O₅ polyhedra by O-cpia/btb mixed linkers. 2 also exhibits a 3D structure based on trinuclear clusters [Cu₃(COO)₄] SBUs, bridged with Cu(1)O₃N₂ and Cu(2)O₄ polyhedra via O-cpia/bpy mixed ligands. 3 shows a 2D network consisting of tetranuclear clusters [Ni₄(μ₃-OH)₂] SBUs, which are bridged with Ni(1)O₄N₂ and Ni(2)O₆ through O-cpia ligands. It is worth noting that 4, with a 3D structure, is generated from the binuclear clusters [Ni₂(COO)₄] (Ni(1)O₄N) and mononuclear metal Ni(2) cores (Ni(2)O₄N₂) as SBUs, and bridged by O-cpia/bpy mixed ligands. Meanwhile, the degradation of dyes (RhB) by the complexes under visible light irradiation was studied. 1–4 are semiconducting in nature, with E_g of 1.30 eV (1), 1.78 eV (2), 2.85 eV (3) and 2.14 eV (4). Cu(ii) complexes 1 and 2 are highly efficient photocatalysts for the degradation of RhB under visible light irradiation.

Four Cu(ii)/Ni(ii)-metal–organic frameworks were constructed from different homometallic clusters by O-cpia/N-ligands. Cu(ii)-complexes show highly efficient photocatalysts for the degradation of RhB under visible light irradiation.     

Application of temperature-controlled chiral hybrid structures constructed from copper(ii)-monosubstituted Keggin polyoxoanions and copper(ii)-organoamine complexes in enantioselective sensing of tartaric acid

Temperature usually occupies a crucial position in the construction of chiral compounds. By controlling the temperature of the reaction system, chiral and non-chiral compounds can be designed and synthesized. Given the above, three new chiral and non-chiral compounds based on copper(ii) monosubstituted polyoxoanions and Cu(en) complexes (en = ethylenediamine), d/l-[Cu(H₂O)(en)₂]₂{[Cu(H₂O)₂(en)][SiCuW₁₁O₃₉]}·5H₂O (1, d-1 and l-1) and [Cu(H₂O)(en)₂]{[Cu(en)₂]₂[SiCuW₁₁O₃₉]}·2.5H₂O (2), were successfully synthesized under hydrothermal conditions. The main synthesis conditions of compound 1 (d-1 and l-1) and compound 2 are the same, however, the only difference is that the reaction temperatures are 80 °C and 140 °C, respectively. What''s more, compounds 1 and 2 can form a 1D chiral chain by Cu–O and W/Cu–O–W/Cu bonds, respectively, and further obtain a 3D-supramolecular framework through hydrogen bonding interaction. Meanwhile, due to the asymmetry of chiral compound 1, optical second-harmonic generation (SHG) was used to investigate the second-order nonlinear optical effect and it was found that the observed SHG efficiency of compound 1 is 0.3 times that of urea. To further investigate the chiral properties, d-1 and l-1 were used in the electrochemical enantioselective sensing of d-/l-tartaric acid (d-/l-tart) molecules, respectively, which demonstrates that d-1 and l-1 have a good application prospect in sensing chiral substances.

A pair of temperature-controlled chiral compounds, d- and l-[Cu(en)₂(H₂O)]₂{[Cu(en)(H₂O)₂][SiCuW₁₁O₃₉]}·5H₂O (en = ethanediamine) are isolated by hydrothermal method, having a good application prospect in sensing d-/l-tartaric acid.     

Structural diversity in the coordination compounds of cobalt,nickel and copper with N-alkylglycinates: crystallographic and ESR study in the solid state

Reactions of N-methylglycine (HMeGly), N-ethylglycine-hydrochloride (H₂EtGlyCl) and N-propylglycine-hydrochloride (H₂PrGlyCl) with cobalt(ii), nickel(ii) and copper(ii) ions in aqueous solutions resulted in ten new coordination compounds [Co(MeGly)₂(H₂O)₂] (1), [{Co(MeGly)₂}₂(μ-OH)₂]·2H₂O (1d), [Cu(MeGly)₂(H₂O)₂] (2α), [Co(EtGly)₂(H₂O)₂] (3), [Ni(EtGly)₂(H₂O)₂] (4), [Cu(μ-EtGly)₂]_n (5p), [Co(PrGly)₂(H₂O)₂] (6), [Ni(PrGly)₂(H₂O)₂] (7), and two polymorphs of [Cu(PrGly)₂(H₂O)₂] (8α and 8β). Compounds were characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, thermal analysis and X-band electron spin resonance (ESR) spectroscopy. These studies revealed a wide range of structural types including monomeric, dimeric and polymeric architectures, as well as different polymorphs. In all monomeric compounds, except 2α, and in the coordination polymer 5p hydrogen bonds interconnect the molecules into 2D layers with the alkyl chain pointing outward of the layer. In 2α and in the dimeric compound 1d hydrogen bonds link the molecules into 3D structures. 1d with cobalt(iii), and 4 and 7 with nickel(ii) are ESR silent. The ESR spectra of 1, 3 and 6 are characteristic for paramagnetic high-spin cobalt(ii). The ESR spectra of all copper(ii) coordination compounds show that the unpaired copper electron is located in the d_x²−y² orbital, being in agreement with the elongated octahedral geometry.

Interactions in copper, nickel and cobalt complexes with N-methyl-, N-ethyl- and N-propylglycinate: monomers, dimer and polymers.     

One-dimensional chain structures of hexanuclear uranium(iv) clusters bridged by formate ligands

Three one-dimensional chain structures of uranium(iv) hexanuclear clusters have been synthesized under hydrothermal/solvothermal conditions. Crystallographic studies disclose that the structures of [U₆O₄(OH)₄(HCOO)₁₂(H₂O)]·3H₂O (1a), [U₆O₄(OH)₄(HCOO)₁₂(HCOOH)(H₂O)]·3H₂O (1b) and (H₆C₅N)₂[U₆O₄(OH)₄(HCOO)₁₄(H₅C₅N)] (2) contain a U(iv) hexanulear core [U₆(μ₃-OH)₄(μ₃-O)₄]¹²⁺ which is decorated by terminal HCOO⁻ ligands and water (1a, 1b), HCOOH (1b) or pyridine molecules (2). These hexanuclear U(iv) clusters are further linked into zig–zag 1-D chain structures via bridging HCOO⁻ ligands. UV-vis-NIR spectra, together with bond valence calculations, indicate that all U atoms in three compounds exist as U(iv). Magnetic susceptibility data reveal that compound 2 exhibits paramagnetic characteristics.

Three one-dimensional chain structures of uranium(iv) hexanuclear clusters have been synthesized under hydrothermal/solvothermal conditions.     

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.     

High Tm linear poly(l-lactide)s prepared via alcohol-initiated ROPs of l-lactide

Alcohol-initiated ROPs of l-lactide were performed in bulk at 160 °C for 72 h with variation of the catalyst or with variation of the initiator (aliphatic alcohols). Spontaneous crystallization was only observed when cyclic Sn(ii) compounds were used as a catalyst. Regardless of initiator, high melting crystallites with melting temperatures (T_m) of 189–193 °C were obtained in almost all experiments with Sn(ii) 2,2′-dioxybiphenyl (SnBiph) as catalyst, even when the time was shortened to 24 h. These HT_m poly(lactide)s represent the thermodynamically most stable form of poly(l-lactide). Regardless of the reaction conditions, such high melting crystallites were never obtained when Sn(ii) 2-ethylhexanoate (SnOct₂) was used as catalyst. SAXS measurements evidenced that formation of HT_m poly(l-lactide) involves growth of the crystallite thickness, but chemical modification of the crystallite surface (smoothing) seems to be of greater importance. A hypothesis, why the “surface smoothing” is more effective for crystallites of linear chains than for crystallites composed of cycles is discussed.

By variation of reaction conditions and catalysts a cyclic tin(ii) compound was found, which enables synthesis of high melting (>190 °C) poly(l-lactide) via ROP of l-lactide, whereas the technically used catalyst SnOct₂ does not show such a performance.     

Pu(iii) and Cm(iii) in the presence of EDTA: aqueous speciation,redox behavior,and the impact of Ca(ii)

The impact of calcium on the solubility, redox behavior, and speciation of the An(iii)–EDTA (An = Pu or Cm) system under reducing, anoxic conditions was investigated through batch solubility experiments, X-ray absorption spectroscopy (XAS), density functional theory (DFT), and time-resolved laser fluorescence spectroscopy (TRLFS). Batch solubility experiments were conducted from undersaturation using Pu(OH)₃(am) as the solid phase in contact with 0.1 M NaCl–NaOH–HCl–EDTA–CaCl₂ solutions at [EDTA] = 1 mM, pH_m = 7.5–9.5, and [CaCl₂] ≤20 mM. Additional samples targeted brine systems represented by 3.5 M CaCl₂ and WIPP simulated brine. Solubility data in the absence of calcium were well-described by Pu(iii)–EDTA thermodynamic models, thus supporting the stabilization of Pu(iii)–EDTA complexes in solution. Cm(iii)–EDTA TRLFS data suggested the stepwise hydrolysis of An(iii)-EDTA complexes with increasing pH, and current Pu(iii)-EDTA solubility models were reassessed to evaluate the possibility of including Pu(iii)–OH–EDTA complexes and to calculate preliminary formation constants. Solubility data in the presence of calcium exhibited nearly constant log m(Pu)_tot, as limited by total ligand concentration, with increasing [CaCl₂]_tot, which supports the formation of calcium-stabilized Pu(iii)–EDTA complexes in solution. XAS spectra without calcium showed partial oxidation of Pu(iii) to Pu(iv) in the aqueous phase, while calcium-containing experiments exhibited only Pu(iii), suggesting that Ca–Pu(iii)–EDTA complexes may stabilize Pu(iii) over short timeframes (t ≤45 days). DFT calculations on the Ca–Pu(iii)–EDTA system and TRLFS studies on the analogous Ca–Cm(iii)–EDTA system show that calcium likely stabilizes An(iii)–EDTA complexes but can also potentially stabilize An(iii)–OH–EDTA species in solution. This hints towards the possible existence of four major complex types within Ca–An(iii)–EDTA systems: An(iii)–EDTA, An(iii)–OH–EDTA, Ca–An(iii)–EDTA, and Ca–An(iii)–OH–EDTA. While the exact stoichiometry and degree of ligand protonation within these complexes remain undefined, their formation must be accounted for to properly assess the fate and transport of plutonium under conditions relevant to nuclear waste disposal.

Combined advanced spectroscopy and solubility studies provide evidence for the formation of novel calcium-containing and hydrolyzed (Cm,Pu)(iii)–EDTA complex(es).     

Structural conversion of three copper(ii) complexes with snapshot observations based on the different crystal colours and morphology

Three novel Cu(ii) complexes [Cu₂(L)₂(MeOH)₂] (1), [Cu₂(L)₂(H₂O)₂] (2) and [CuL(H₂O)] (3) (L = (E)-2-((2-hydroxy-4-methoxybenzylidene)amino)acetic acid) have been obtained in different time scales of reaction processing. Complexes 1 and 2 are kinetically controlled products and 3 is a thermodynamically stable product. Single crystal X-ray diffraction analyses revealed that 1 and 2 are binuclear complexes except for different coordination solvents. 3 is a mononuclear complex. Complex 1 is mainly obtained in methanol solution, while 2 and 3 are stable in aqueous solvents. Based on the understanding of crystal structures of the three complexes, reversibly transforming crystal 2 to crystal 1 at room temperature has been realised, which has been confirmed by the change of colours and morphology measured by SEM. The research work is very important for controllable synthesis of coordination complexes.

Structural conversion of three novel Cu(ii) complexes [Cu₂(L)₂(MeOH)₂] (1), [Cu₂(L)₂(H₂O)₂] (2) and [CuL(H₂O)] (3) (L = (E)-2-((2-hydroxy-4-methoxybenzylidene)amino)acetic acid) in different time scales of reaction processing.     

An investigation of two copper(ii) complexes with a triazole derivative as a ligand: magnetic and catalytic properties

Two new copper(ii) complexes [Cu₂(L)₂(OAc)₂(H₂O)₂] (1) (L = 3-methyl-5-pyridin-2-yl-1,2,4-triazole) and [CuL₂] (2) were prerared and thoroughly studied. The complexes are able to selectively catalyze the oxidation of styrene towards benzaldehyde and of cyclohexane to KA oil. The 2D coordination polymer 1 showed an antiferromagnetic behaviour attributed to the intrachain magnetic coupling.

Two copper(ii) complexes were investigated as catalysts for selective oxidation of styrene to benzaldehyde and of cyclohexane to KA oil.     

Three new metal coordination polymers of bifunctional imidazolate/tetrazolate bridges: the only example of a three-dimensional framework based on rare [Co4(μ3-OH)2(μ2-Cl)2]4+ mixed oxo-chloro-clusters

Three new metal coordination polymers [Ni(μ₂-L)₂(H₂O)₂]_n(1, HL = 1-tetrazole-4-imidazole-benzene), [Co(μ₂-L)₂]_n (2), and [Co₄(μ₃-OH)₂(μ₂-Cl)₂(μ₅-L)₂(μ₂-L)₂]_n·7nH₂O (3) were hydrothermally synthesized and structurally characterized. 1 displays a neutral [Ni(μ₂-L)₂(H₂O)₂]_n chain built up from the Ni²⁺ ions bridged by deprotonated L⁻ ligands, while 2 shows another rare neutral [Co(μ₂-L)₂]_n chain based on Co²⁺ ions connected by two different coordination modes of the L⁻ ligand. 3 exhibits a rare [Co₄(μ₃-OH)₂(μ₂-Cl)₂]⁴⁺ mixed oxo-chloro-cluster-based three-dimensional framework with large elliptical channels, which are filled by unprecedented chilopod [(H₂O)₇]_n chains. Both 1 and 2 show antiferromagnetic behavior, while 3 exhibits unusual spin-canting.

The interconnection of rare [Co₄(μ₃-OH)₂(μ₂-Cl)₂]⁴⁺ mixed oxo-chloro-clusters and bifunctional bridges gives a new three-dimensional framework with unusual spin-canting behavior.     

Synthesis,crystal structures,DNA interactions,and antitumor activity of two new dinuclear copper(ii) complexes with thiazole ligand

Two new dinuclear copper(ii) complexes, [Cu(ambt)₂(cnba)₄] (1) and [Cu(ambt)₂(clba)₄] (2) were synthesized with 2-amino-6-methoxybenzothiazole (ambt) as the main ligand. The structures of the two complexes were characterized by single-crystal XRD. The binding between CT-DNA (calf thymus DNA) and the complexes was evaluated by viscometry, electronic absorption, and fluorescence spectroscopy, and the binding constants were calculated using the Stern–Volmer equation. The complexes were intercalatively bound to CT-DNA, and [Cu(ambt)₂(clba)₄] having a greater binding constant than [Cu(ambt)₂(cnba)₄]. The two complexes had better antitumor properties against HepG2 (human hepatocellular carcinoma), A549 (human lung carcinoma), and HeLa (human cervical carcinoma) tumor cell lines than their respective ligands and cisplatin. Furthermore, [Cu(ambt)₂(clba)₄] had a stronger inhibitory ability on the three types of tumor cells than [Cu(ambt)₂(cnba)₄], which is congruent with the binding power of the complexes with DNA. Flow cytometry revealed that [Cu(ambt)₂(cnba)₄] and [Cu(ambt)₂(clba)₄] could trigger apoptosis or necrosis, arrest the HepG2 cell cycles, and cause G0/G1-phase cells to accumulate.

Two new dinuclear copper(ii) complexes, [Cu(ambt)₂(cnba)₄] (a) and [Cu(ambt)₂(clba)₄] (b) were synthesized with 2-amino-6-methoxybenzothiazole (ambt) as the main ligand.     

Synthesis,structures, and catalytic efficiency in ring opening polymerization of rac-lactide with tridentate vs. bidentate cobalt(ii), zinc(ii), and cadmium(ii) complexes containing N-substituted N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)amine ligands

A series of Co(ii), Zn(ii), and Cd(ii) complexes supported by 1-(3,5-dimethyl-1H-pyrazol-1-yl)-N-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-N-(furan-2-ylmethyl)methanamine (L_A) and N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-4-isopropylaniline (L_B) were synthesized. The direct chelation of CoCl₂·6H₂O, ZnCl₂, and CdBr₂·4H₂O by the ligands produced [L_nMX₂] (L_n = L_A or L_B; M = Zn or Co, with X = Cl; M = Cd, with X = Br) complexes in high yields. Structural studies revealed that [L_BCoCl₂] and [L_BZnCl₂] adopted distorted tetrahedral geometries, as L_B coordinated the metal centers in a bidentate fashion, while L_A coordinated the metal centers in a tridentate fashion through the nitrogen atoms of the pyrazole and amine moieties, so that [L_ACoCl₂] and [L_AZnCl₂] exhibited trigonal bipyramidal geometries and [L_ACdBr₂] a square pyramidal geometry. [L_BCdBr₂] has two Cd-containing structures per unit cell, whereby one Cd center adopted a distorted tetrahedral geometry and the other exhibited square bipyramidal geometry. The in situ-generated alkyl derivatives of the synthesized complexes were assessed in the ring-opening polymerization of rac-lactide. Heterotactic polylactides (PLAs) were furnished with all complexes. The [L_BZnCl₂]/MeLi system produced PLA with a superior heterotactic bias (P_r up to 0.94) at −25 °C. PLAs with wide-ranging polydispersity indices (1.16–2.23) and low molecular weights were produced in all cases, irrespective of the specific M(II) center and ancillary ligand utilized.

Co(ii), Zn(ii), and Cd(ii) complexes supported by bis-pyrazolyl ligands were applied to the ring-opening polymerization of rac-lactide to produce heterotactic polylactides (PLAs) with superior heterotactic bias i.e. P_r up to 0.94 at −25 °C.     

Sonochemical synthesis of a trinuclear Cu(ii) complex with open coordination sites for the differentiable optical detection of volatile amines

A discrete trinuclear Cu(ii) complex, namely, [Cu₃(pzdc)₂(dpyam)₂(H₂O)₄] (1) (H₃pzdc = pyrazole-3,5-dicarboxylic acid, dpyam = 2,2′-dipyridylamine) was simply synthesized by the sonochemical process and structurally characterized. The single-crystal X-ray diffraction analysis revealed that three adjacent Cu(ii) centers are linked via two bridging pzdc ligands to form a trinuclear Cu(ii) unit. Each trinuclear Cu(ii) unit contains open coordination sites with two trigonal bipyramidal Cu(ii) centers and one elongated octahedral geometry. Moreover, the open coordination site of 1 was occupied by a small molecule, leading to the guest-induced structural transformation with chromism that was verified by FT-IR, UV-vis diffuse reflectance spectra, elemental analysis, PXRD, and SEM techniques. Compound 1 exhibits color change along with structural transformation in methanol media and after the dehydration process. Also, 1 shows different color responses after exposure to different amine vapors. In addition, compound 1 was conveniently deposited onto a filter paper by a sonochemical method used as a portable test strip for the discriminative qualitative detection of amines.

A trinuclear Cu(ii) complex with open coordination sites for the differentiable optical detection of volatile amines.     

Facile transmetallation of [SbIII(DOTA)]− renders it unsuitable for medical applications

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed. The Sb(iii) ion in Na[Sb(DOTA)]·4H₂O shows an approximately square antiprismatic coordination geometry that is close to superimposable to the Bi(iii) geometry in [Bi(DOTA)]⁻ in two phases containing this anion, Na[Bi(DOTA)]·4H₂O, [H₃O][Bi(DOTA)]·H₂O for which structures are also described. Interestingly, DOTA itself in [(H₆DOTA)]Cl₂·4H₂O·DMSO shows the same orientation of the N₄O₄ metal binding cavity reflecting the limited flexibility of DOTA in an octadentate coordination mode. In 8-coordinate complexes it can however accommodate M(iii) ions with r_ion spanning a relatively wide range from 87 pm (Sc(iii)) to 117 pm (Bi(iii)). The larger Bi³⁺ ion appears to be the best metal–ligand size match since [Bi(DOTA)]⁻ is associated with greater complex stability. In the solution state, [Sb(DOTA)]⁻ is extremely susceptible to transmetallation by trivalent ions (Sc(iii), Y(iii), Bi(iii)) and, significantly, even by biologically important divalent metal ions (Mg(ii), Ca(ii), Zn(ii)). In all cases just one equivalent is enough to displace most of the Sb(iii). [Sb(DOTA)]⁻ is resistant to hydrolysis; however, since biologically more abundant metal ions easily substitute the antimony, DOTA complexes will not be suitable for deployment for the delivery of the, so far unexploited, theranostic isotope pair ¹¹⁹Sb and ¹¹⁷Sb.

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed.     

LNA units present in [RP-PS]-(DNA#LNA) chimeras enhance the thermal stability of parallel duplexes and triplexes formed with (2′-OMe)-RNA strands

The results of CD measurements indicate that 2-4 LNA units distributed along 12 nt P-stereodefined phosphorothioate [R_P-PS]-(DNA#LNA) chimeras impose a C3′-endo conformation on the 2′-deoxyribonucleosides. Under neutral and slightly acidic conditions homopurine [R_p-PS]-(DNA#LNA) hybridizes with 9–12 nt Hoogsteen-paired (2′-OMe)-RNA strands to form parallel duplexes, which are thermally more stable than the reported earlier analogous complexes containing LNA-free [R_P-PS]-DNA oligomers (ΔT_m = 7 °C per LNA unit at pH 5.4). Upon addition of the corresponding Watson–Crick-paired (2′-OMe)-RNA strands, parallel triplexes are formed with further increased thermal stability.

3′-O-(2-Thio-1,3,2-oxathiaphospholane) derivatives of 5′-O-DMT-LNA-nucleosides were used to prepare P-stereodefined (R_P-PS)-DNA#LNA chimeras, which form thermally stable parallel complexes with (2′-OMe)-RNA matrices.     

Bismuth subsalicylate,a low-toxicity catalyst for the ring-opening polymerization (ROP) of l-lactide (l-LA) with aliphatic diol initiators: synthesis,characterization, and mechanism of initiation

The ring-opening polymerization (ROP) of l-lactide (l-LA) was induced by the catalytic action of bismuth subsalicylate (BiSS) using linear aliphatic diols [HO(CH₂)_nOH, where n = 2, 3, 4, 5, 6, and 8] as initiators and chain transfer agents. The theoretical and experimental degree of polymerization (DP) in all samples of α,ω-hydroxy telechelic poly(l-lactide) (HOPLLAOH) had a good agreement in all samples, an effect attributed to the interaction of BiSS with HO(CH₂)_nOH inducing a transfer reaction. HOPLLAOH was synthesized and characterized by a range of analytical techniques, confirming the insertion of methylene groups from the initiator into the main chain of the polyester. The glass-transition temperature (T_g) of HOPLLAOH was found to be proportional to the number of methylene groups present in the diol. Various parameters regarding the ROP of l-LA were studied, such as temperature, time of reaction, amount of catalyst, and the nature of the diols. A kinetic study of the reaction allowed the determination of the rate constants (k) and activation energy (E_a). A mechanism of initiation is proposed based on a computational study using density functional theory (DFT), evidencing the role of the alkyl diol as an initiator, producing an alkoxide (Bi–OROH). This species then acts as a nucleophile, attacking the carbonyl group, inducing its insertion, and ultimately completing the ring-opening of l-LA.

Bismuth subsalicylate (BiSS) acted as a catalyst in the ring-opening polymerization of l-lactide (l-LA) in the presence of alkyl diols as initiators.