Phen Ligands Research Articles

Cytotoxicity, genotoxicity and mutagenicity of mixed ternary mononuclear Mg complex based on valproic acid with 1,10-phenanthroline in Saccharomyces cerevisiae and V79 cells.

Valproic acid (VA) is a widely used drug for the treatment of diseases affecting the central nervous system. Due to its epigenetic modulatory potential, it has been studied for possible therapeutic application in anticancer therapies. However, the VA exhibits different side effects in its application. Thus, synthetic coordination complexes with valproate can generate promising candidates for new active drugs with reduced toxicity. In this sense, we investigated the genotoxic and mutagenic potential of the sodium valproate and of the mixed ternary mononuclear Mg complex based on VA with 1,10-phenanthroline (Phen) ligand - [Mg (Valp)2Phen], in Saccharomyces cerevisiae and V79 cells. The MTT and clonal survival assays in V79 cells indicated that the Mg complex has higher cytotoxicity than sodium valproate. A similar cytotoxicity profile is observed in yeast. This fact is possibly due to the intercalation capacity of [Mg(Valp)2Phen], inducing DNA strand breaks, as observed in the comet assay and micronucleus test. In this sense, members of the NER, HR, NHEJ and TLS repair pathways are required for the repair of DNA lesions induced by [Mg(Valp)2Phen]. Interestingly, BER proteins apparently increase the cytotoxic potential of the drug. Furthermore, the [Mg(Valp)2Phen] showed higher cytotoxicity in V79 cells and yeast when compared to sodium valproate indicating applicability as a cytotoxic agent.

Comparative Study on the Proton Conduction Behaviors of Two Acidic Amphiphilic and Hydrophilic Coordination Compounds in Nafion Composite Membranes.

The acidic amphiphilic compound H[Co(H2L1)(HL1)(phen)]·3H2O (H4(Co-L1), H3L1 = 5-(3', 5'-dicarboxylphenyl)-pyridine-2-carboxylic, phen = phenanthroline) and the hydrophilic compound [Ni(HL2)(H2O)5]·H2O (H(Ni-L2), H3L2 = 5-(3',5'-dicarboxylphenyl)-pyridine-3-carboxylic) were synthesized via hydrothermal reactions at acidic conditions. The acidity of H4(Co-L1) is stronger than of H(Ni-L2); while the hydrogen bond continuity in H4(Co-L1) extended monodirectionally, which is smaller compared to the three-directional extension observed in H(Ni-L2). The proton conduction behaviors of these two compounds as fillers of Nafion composite membranes have been investigated. The results indicate that the optimal doping amounts of H4(Co-L1) and H(Ni-L2) are 2 and 1%, respectively; the proton conductivities of H4(Co-L1)/Nafion-2 and H(Ni-L2)/Nafion-1 composite membranes are 0.243 and 0.212 S·cm-1, respectively, which are approximately 50.2 and 30.6% higher than that of pure Nafion membrane, respectively. A higher doping amount of H4(Co-L1) can be attributed to its hydrophobic phen ligand, which promotes compatibility with Nafion membrane and reduces aggregation. Hydrogen bond continuity has a more significant effect on proton conductivity than acidity at relatively low doping amounts; conversely, this relationship reverses at relatively high doping amounts.

The Synthesis, Structural Characterization, and DFT Calculation of a New Binuclear Gd(III) Complex with 4-Aacetylphenoxyacetic Acid and 1,10-Phenanthroline Ligands and Its Roles in Catalytic Activity.

A new binuclear Gd(III) complex, [Gd2(L)6(Phen)2]·4H2O, was synthesized via the reaction of gadolinium(III) nitrate hexahydrate, 4-acetylphenoxyacetic acid (HL), NaOH, and 1,10-phenanthroline (Phen) in a solution of water-ethanol (v:v = 1:1). The Gd(III) complex was characterized using IR, UV-vis, TG-DSC, fluorescence, and single-crystal X-ray diffraction analyses. The results showed that the Gd(III) complex crystallizes in the triclinic system, space group P-1, and each Gd(III) ion was coordinated with two nitrogen atoms (N1, N2, or N1a, and N2a) from two Phen ligands and seven oxygen atoms (O1, O2, O7a, O9, O8, O8a, O10a, or O1a, O2a, O7, O8, O8a, O9a, and O10) from six L ligands, respectively, forming a nine-coordinated coordination mode. The Gd(III) complex molecules formed a one-dimensional chained and three-dimensional network structure via benzenering π-π stacking. The Hirschfeld surface analysis and the calculations of the electron density distributions of the frontier molecular orbitals of the Gd(III) complex were performed. The catalytic activities of the photocatalytic CO2 reduction and benzyl alcohol oxidation using the Gd(III) complex as a catalyst were performed. The results of the photocatalytic CO2 reduction showed that the yield and the selectivity of CO reached 41.5 μmol/g and more than 99% after four hours, respectively. The results of the benzyl alcohol oxidation showed that the yield of benzaldehyde was 45.7% at 120 °C with THF as the solvent under 0.5 MPa O2 within 2 h.

Hydrothermal syntheses, structures and properties of two zinc complexes based on an azobenzene carboxylate ligand

Abstract Two zinc complexes [Zn(LH)2(phen)] (1) and [Zn(L)(H2O)] n (2) (LH− = 2-hydroxy-5-((3-nitrophenyl)azo)-benzoate, phen = 1,10-phenanthroline) were synthesized by hydrothermal methods and characterized by elemental analysis and IR spectroscopy. Complexes 1 and 2 crystallize in mononuclear and polymeric structures, respectively, where ligands L 2− are coordinated to the zinc ions via their carboxylate and phenolate groups in η 2,μ 2,κ 2 and η 2,μ 2,κ 1 mode, respectively. Introduction of the auxiliary chelating phen ligand results in the chelation of the zinc ions in 1 through both the phen ligand and the carboxylate group of the first LH− anion assisted further by the monodentate carboxylate group of the second LH− anion. In complex 2 the L 2− anions act as tridentate ligands utilizing their carboxylate and phenolate groups to coordinate to three zinc ions. The phenolate oxygen atom bridges two zinc ions resulting in the generation of a layer structure. Fluorescence measurements have indicated that complexes 1 and 2 exhibit similar luminescence emissions around 393 and 387 nm, respectively, which originate from intra-ligand π-π* transitions. The emission intensities were strengthened relative to the sodium complex NaLH owing to the enhancement of the rigidity of the aromatic system through the coordination interactions of the ligands with the more tightly bound zinc ions. Furthermore, the suspension of complex 2 can be used to selectively detect Fe3+ cations via the luminescence quenching process.

Elucidation of the Pyridine Ring-Opening Mechanism of 2,2'-Bipyridine or 1,10-Phenanthroline Ligands at Re(I) Carbonyl Complexes.

The cleavage of the C-N bonds of aromatic heterocycles, such as pyridines or quinolines, is a crucial step in the hydrodenitrogenation (HDN) industrial processes of fuels in order to minimize the emission of nitrogen oxides into the atmosphere. Due to the harsh conditions under which these reactions take place (high temperature and H2 pressure), the mechanism by which they occur is only partially understood, and any study at the molecular level that reveals new mechanistic possibilities in this area is of great interest. Herein, we unravel the pyridine ring-opening mechanism of 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) ligands coordinated to the cis-{Re(CO)2(N-RIm)(PMe3)} (N-RIm= N-alkylimidazole) fragment under mild conditions. Computational calculations show that deprotonation of the pyridine ring, once dearomatized, is crucial to induce ring contraction, triggering extrusion of the nitrogen atom from the ring and cleavage of the C-N bond. It is noteworthy that different products (regioisomers) are obtained depending on whether the ligand used is bipy or phen due to the additional rigidity and stability conferred by the central ring of the phen ligand, an issue also addressed and clarified computationally. Strong support for the proposed mechanism is provided by the characterization and isolation, including three single-crystal X-ray diffraction structures, of several of the proposed reaction intermediates.

3,4-selective polymerization of isoprene by iron-based system: The key role of borate salts for enhancing catalytic activities and broadening 1,10-phenanthroline ligand scope

The catalytic system of iron(III) compound/alkylaluminum/1,10-phenothroline(Phen) has been long disclosed for efficient 3,4-selective polymerization of isoprene to achieve semi-crystalline 3,4-polyisoprene product, that finds important application in the current tire industry. Nevertheless, such a system is highly sensitive to the steric nature of Phen ligands, even a subtle variation (e.g. introducing methyl group to its 2,9-position) will result in significantly decreased catalytic activities. In this research, we disclose a facile method, i.e. in-situ addition of borate salts, that can well address such a long unsolved issue. By doing such, the pristine catalytic activities were able to be greatly enhanced (ca. 4-fold higher) without damaging the selectivity of the active species. Such a method was also applicable for various substituted Phen ligands, such as Phen2,9-(nBu)2, Phen2,9-(sBu)2, Phen2,9-(tBu)2, Phen2,9-(nHex)2, etc., which greatly broadens the ligand scope of such iron(III) based catalytic system. Mechanistic studies revealed that the attraction of alkyl group by borate salts to form the cationic active species might play a governing role in enhancing the activities.

Regio‐ and Stereo‐Selective Synthesis of (E)‐β‐Alkenyl Boronates by Phosphene‐Free CuI‐Catalyzed Hydroboration and Carboboration of Alkynes and Access to Allyl‐Vinyl Ethers

AbstractA convenient and operationally trivial protocol to access synthetically versatile vinylboronates through CuI catalyzed hydroboration and carboboration of alkynes utilizing bis(pinacolato)diboron (B2pin2) as the boron precursor in a 1, 10‐phenanthroline (phen) ligand environment is reported. This is a highly efficient and practical method for the synthesis of regio‐ and stereoselective (E)‐β‐vinylboronates from simple aromatic and aliphatic alkynes. These organoboron compounds have further been utilized for the synthesis of allyl‐vinyl ethers, which are potential starting materials for the Claisen rearrangement via an improved CuII mediated coupling of allyl alcohols and vinylboronates. The vinylboronates were also subjected to Suzuki‐Miyaura cross coupling reaction, allowing access to the corresponding tri‐ and tetra‐substituted alkenes with good isolated yields.

Introduction of functionality into a Tb(III)-organic framework via mixed-ligand strategy for selective C2H2 capture and ratiometric Cr(VI) detection

Introduction of porosity and fluorescent properties into lanthanide metal–organic frameworks (MOFs) with rational design to achieve multifunctional use is of great significance from the energy and environmental viewpoint. In this study, a microporous Tb(III)-based MOF with the formula of {[Tb2(oba)3(Phen)2](DMF)2(H2O)4}n (1) was solvothermally prepared via using the mixed ligands of 1,10-phenanthroline (Phen) and 4,4′-oxybis(benzoic acid) (H2oba) as organic connecters. The structural evaluation results indicate that complex 1 is composed of binuclear Tb2(CO2)6(Phen)2 clusters which are extended by the oba2− ligands to afford a two-fold interpenetrated framework with one-dimensional microporous channels along the b-axis. Gas sorption studies show that the activated 1 demonstrates a high ideal adsorption solution theory (IAST) sorption selectivity of 7.4 toward C2H2 in a C2H2/CO2 gas mixture, which are further supported by the dynamic breakthrough experiments. The grand canonical Monte Carlo (GCMC) simulation results indicate that the synergistic effects of the H-bond interactions of C2H2 with oba2− ligands and the C–H···π interactions with Phen ligand contribute to the strong binding of the framework toward C2H2 molecules. What's more, the luminescent measurements reveal that the emission of 1 features both the characteristic peaks of Phen ligand and Tb(III) ion, which could be further applied as a self-calibrating sensor for the Cr(VI) detection in water. To the best of our knowledge, complex 1 represents the first example of Tb-MOF holding such a high C2H2/CO2 selectivity together with ratiometric Cr(VI) detection performances.

Probing a Major DNA Weakness: Resolving the Groove and Sequence Selectivity of the Diimine Complex Λ‐[Ru(phen)2phi]2+

AbstractThe grooves of DNA provide recognition sites for many nucleic acid binding proteins and anticancer drugs such as the covalently binding cisplatin. Here we report a crystal structure showing, for the first time, groove selectivity by an intercalating ruthenium complex. The complex Λ‐[Ru(phen)2phi]2+, where phi=9,10‐phenanthrenediimine, is bound to the DNA decamer duplex d(CCGGTACCGG)2. The structure shows that the metal complex is symmetrically bound in the major groove at the central TA/TA step, and asymmetrically bound in the minor groove at the adjacent GG/CC steps. A third type of binding links the strands, in which each terminal cytosine base stacks with one phen ligand. The overall binding stoichiometry is four Ru complexes per duplex. Complementary biophysical measurements confirm the binding preference for the Λ‐enantiomer and show a high affinity for TA/TA steps and, more generally, TA‐rich sequences. A striking enantiospecific elevation of melting temperatures is found for oligonucleotides which include the TATA box sequence.

Probing a Major DNA Weakness: Resolving the Groove and Sequence Selectivity of the Diimine Complex Λ-[Ru(phen)2 phi]2.

The grooves of DNA provide recognition sites for many nucleic acid binding proteins and anticancer drugs such as the covalently binding cisplatin. Here we report a crystal structure showing, for the first time, groove selectivity by an intercalating ruthenium complex. The complex Λ-[Ru(phen)2 phi]2+ , where phi=9,10-phenanthrenediimine, is bound to the DNA decamer duplex d(CCGGTACCGG)2 . The structure shows that the metal complex is symmetrically bound in the major groove at the central TA/TA step, and asymmetrically bound in the minor groove at the adjacent GG/CC steps. A third type of binding links the strands, in which each terminal cytosine base stacks with one phen ligand. The overall binding stoichiometry is four Ru complexes per duplex. Complementary biophysical measurements confirm the binding preference for the Λ-enantiomer and show a high affinity for TA/TA steps and, more generally, TA-rich sequences. A striking enantiospecific elevation of melting temperatures is found for oligonucleotides which include the TATA box sequence.

Correction to “Comparisons of bpy and phen Ligand Backbones in Cr-Mediated (Co-) Electrocatalytic CO2 Reduction”

Correction to “Comparisons of bpy and phen Ligand Backbones in Cr-Mediated (Co-) Electrocatalytic CO₂ Reduction”

Ruthenium(II) complexes with phosphonate-substituted phenanthroline ligands as reusable photoredox catalysts.

Ru(II) complexes with polypyridyl ligands (2,2'-bipyridine = bpy, 1,10-phenanthroline = phen) play a central role in the development of photocatalytic organic reactions. In this work, we synthesized four mixed-ligand [Ru(phen)(bpy)2]2+-type complexes (Ru-Pcat-A) bearing two phosphonate substituents P(O)(OH)(OR) (R = H, Et) attached to the phen core at positions 3,8 (Ru-3,8PH and Ru-3,8PHEt) and 4,7 (Ru-4,7PH and Ru-4,7PHEt) of the heterocycle in high yields (87-99%) and characterized them using spectral methods. Single crystal X-ray diffraction was employed to determine the coordination mode of the ditopic phen ligand in Ru-4,7PH. This complex exists as the neutral species and forms a 1D hydrogen-bonded framework in the crystals. The light absorption characteristics were found to be similar for all complexes prepared in this work. However, the emission maxima in aqueous solutions were significantly affected by the substitution of the heterocycle, ranging from 629 nm for Ru-4,7PH to 661 nm for Ru-3,8PHEt. The emission quantum yields in Ar-saturated deionized water showed a strong dependence on the substitution pattern of the phen ligand, with maximal values reaching approximately 0.11 for Ru-4,7PHEt and Ru-4,7PH, which is twice as high as that of the classical [Ru(bpy)3]2+ complex (Ru-bpy). The photocatalytic performance of Ru-Pcat-A was investigated using visible light photoredox catalytic transformations of tertiary amines. With Ru-Pcat-A, we achieved the phosphonylation of N-aryl-1,2,3,4-tetrahydroisoquinolines (THIQs) and cyanation of THIQs and N,N-dimethylaniline in methanol, while a mixture of nitromethane/methanol (1 : 1 v/v) proved to be the optimal solvent for conducting the nitromethylation of THIQs. In the majority of the studied reactions, Ru-4,7PHEt exhibited greater efficiency compared to Ru-bpy, and it could be easily separated from the products using water extraction and reused in the next catalytic cycle. We successfully performed seven consecutive nitromethylation and phosphonylation of N-phenyl-1,2,3,4-tetrahydroisoquinoline using the recycled homogeneous photoredox catalyst.

Evaluation of the anionic effect on the formation of biologically active {CuII-phenx; x = 1, 2, 3} fragments - Synthetic and structural variations, antimycobacterial and antiblastoma effects

Two cationic and molecular copper(II) complexes - mixed ligand [{Cu(phen)2benz}{Cu(phen)2Cl}]2+·2Cl-·benz-·H3O+·4·.5H2O (1), [Cu(benz)2phen] (2) (benz- = m-Cl-benzoate anion; phen = 1,10-phenantroline) and [Cu(phen)3]2+·2OTf-·2EtOH (3) (OTf = trifluoromethylsulfonate, triflate anion, CF3SO3-) were synthesized using various synthetic approaches and thoroughly characterized by spectroscopic methods and single crystal X-ray diffraction analysis. The structures of the complexes according to X-ray diffraction data are characterized by a diverse geometric environment of the complexing agent - the cationic form of 1 comprises two structurally nonequivalent moieties: the Cu (1) and Cu (2) complex-forming atoms coordinate, in chelate manner, two phen moieties each and the benz- (1)/Cl- (2) anions, respectively, thus forming different-ligand formula units, a trigonal–bipyramidal {Cu(1)N4Cl} and a pseudo octahedral one {Cu(2)N4O2}. The copper(II) ion in the complex 2 coordinates one phen ligand in a bidentate mode and two benz- anions to produce a distorted planar square environment {CuN2O2}. In complex 3, the copper(II) cation is surrounded by three phenanthroline fragments {Cu(phen)3}2+ and non-coordinated OTf- ions. The results of an EPR study 1 show that in the solid phase, intermolecular exchange interactions that cause exchange narrowing of the spectrum are efficient, whereas in solutions, resolved spectra of copper(II) ion with rhombic symmetry of the g-tensor are observed. An in vitro study of the biological properties of 1–3 toward nonpathogenic mycobacterial strain Mycolicibacterium smegmatis showed an increase in biological effectiveness depending on the structure of complexes (MIC, 1 (2 nmol/disk) > 3 (5 nmol/disk) > 2 (12.5 nmol/disk)). Complex 1 was also tested for antitumor activity against an ovarian adenocarcinoma SKOV3 demonstrated high efficiency: the IC50 value is almost 9 times higher than the activity of cisplatin.

Taming 2,2'-biimidazole ligands in trivalent chromium complexes.

Complete or partial replacement of well-known five-membered chelating 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) ligands with analogous didentate 2,2'-biimidazole (H2biim) provides novel perspectives for exploiting the latter pH-tuneable bridging unit for connecting inert trivalent chromium with cationic partners. The most simple homoleptic complex [Cr(H2biim)3]3+ and its stepwise deprotonated analogues are only poorly soluble in most solvents and their characterization is limited to some solid-state structures, in which the pseudo-octahedral [CrN6] units are found to be intermolecularly connected via peripheral N-H⋯X hydrogen bonds. Moreover, the associated high-energy stretching N-H vibrations drastically quench the targeted near infrared (NIR) CrIII-based phosphorescence, which makes these homoleptic building blocks incompatible with the design of molecular-based luminescent assemblies. Restricting the number of bound 2,2'-biimidazole ligands to a single unit in the challenging heteroleptic [Cr(phen)2(Hxbiim)](1+x)+ (x = 2-0) complexes overcomes the latter limitations and allows (i) the synthesis and characterization of these [CrN6] chromophores in the solid state and in solution, (ii) the stepwise and controlled deprotonation of the bound 2,2'-biimidazole ligand and (iii) the implementation of Cr-centered phosphorescence with energies, lifetimes and quantum yields adapted for using the latter chromophores as sensitizers in promising 'complex-as-ligand' strategies.

Asymmetric electron occupation of transition metals for the oxygen evolution reaction via a ligand-metal synergistic strategy.

The performance of two-dimensional transition-metal (oxy)hydroxides (TMOOHs) for the electrocatalytic oxygen evolution reaction (OER), as well as their large-scale practical applications, are severely limited by the sluggish kinetics of the four-electron OER process. Herein, using a symmetry-breaking strategy, we simulated a complex catalyst composed of a single Co atom and a 1,10-phenanthroline (phen) ligand on CoOOH through density functional theory studies, which exhibits excellent OER performance. The active site Co undergoes a valence oscillation between +2, +3 and even high valence +4 oxidation states during the catalytic process, resulting from the distorted coordination effect after the ligand modification. The induced asymmetry in the electronic states of surrounding nitrogen and oxygen atoms modulates the eg occupation of Co-3d orbitals, which should be of benefit to reduce the overpotential in the OER process. By studying similar catalytic systems, the prominent role of ligands in creating asymmetric electronic structures and in modulating the valence of the active site and the OER performance was reconfirmed. This study provides a new dimension for optimizing the electrocatalytic performance of various TM-ligand complexes.

Spin canting and slow magnetic relaxation in mononuclear cobalt(II) sulfadiazine ternary complexes.

Monomeric [Co(SDZ)2phen] (1) and [Co(SDZ)(bq)Cl] (2) complexes (SDZ = sulfadiazine, phen = 1,10-phenanthroline, and bq = 2,2'-biquinoline) have been synthesized and characterized. X-ray diffraction studies indicate that SDZ acts as a bidentate ligand coordinating through the sulfonamide and the pyrimidine N atoms in both compounds. In complex 1, the coordination sphere consists of two SDZ ligands and a bis-chelating phen ligand, giving rise to a CoN6 coordination sphere. On the other hand, 2 has a CoN4Cl core, with two N-atoms from SDZ and two from the bq ligand. Both compounds have been studied by dc and ac magnetometry and shown to display slow magnetic relaxation under an optimum external dc field (1 kOe) at low temperatures. Moreover, compound 2 displays long range magnetic ordering provided by spin-canted antiferromagnetism, which has been characterized by further field-dependent magnetic susceptibility measurements, FC/ZFC curves, hysteresis loops and frequency-independent ac curves. The signs of the calculated D parameters, positive in 1 and negative in 2, have been rationalized according to the two lowest-lying transitions in the orbital energy diagrams derived from ab initio ligand field theory (AILFT). In a subsequent attempt to reveal the possible hidden zero-field SMM behaviour, Ni(II)-based 3 and Co(II)-doped Ni(II)-based (with a Ni : Co ratio of 0.9 : 0.1) heterometallic compound 2Ni were synthesized.

Phen-2NO, a new C2-symmetric rigid-featured tetradentate ligand, and its application in the asymmetric alkylation reaction of indoles

A new class of C2-symmetric rigid-featured chiral phen ligands that provide the N,N,O,O-tetradentate coordination of the phen moiety and two additional N,N-dioxides were rationally designed and developed.

Ligand Combination Approach in Pd‐Catalyzed Direct C−H Arylation of Benzothiazole and Benzoxazole

AbstractThe use of ligand combination approach in the Pd catalyzed direct C−H arylation of benzothiazole and benzoxazole is demonstrated. The combination of two ligands phenanthroline monohydrate (Phen.H2O) and triphenylphosphine (PPh3) with Pd‐catalyst have offered the best catalytic properties in the C−H bond arylation reactions than either of two ligands employed separately in the reactions. This protocol exhibits a wide substrate scope affording C2 arylated benzothiazole and benzoxazole derivatives in excellent yields. Mechanistic studies including kinetic isotope effect (KIE), H/D exchange and competition experiments show that the C−H bond activation of benzothiazole and benzoxazole is very facile under reaction conditions. Furthermore, different mechanistic pathways originated from the catalytically active species such as Pd(η2‐dba)L (dba=dibenzylidene acetone) and Pd(PPh3)2 were investigated using computational methods. The computational results suggest that the generation of catalytically active species from Pd2(dba)3 is endoergic process and Phen ligand can initiate this step. On the other hand, the presence of PPh3 could be crucial for the oxidative addition of aryl halides which is the rate‐determining step of the reaction.

Rational design of p-ZnS@CN with 3D interconnected hierarchical pore structure through pyrolysis of an organic hybrid zinc thiocyanide for electrochemical lithium storage

3D interconnected porous carbon-coupled metal-sulfide composites have been demonstrated as promising lithium storage materials owing to their large surface areas as well as the acceleration effect to electrochemical kinetics. However, constructing these materials with ordered hierarchical pore structure is still a challenge. To address this issue, we found that the crystals of an organic hybrid zinc thiocyanide [Zn(NCS)2(phen)2] (phen = 1,10-phenanthroline) could become a fluid at 400 °C, and during the melting process, the phen ligand was simulatneously carbonized to form nitrogen-doped carbon materials, while the Zn(NCS)2 species were converted into ZnS quantum dots. This property could allow us to employ a hard template strategy for preparation of a porous p-ZnS@CN composite featuring 3D interconnected hierarchical structure, namely employing SiO2 nanospheres as sacrificial template and [Zn(NCS)2(phen)2] as precursor and thermal treatment this mixture at 400 °C. The as-obtained p-ZnS@CN (p = porous structure, CN = nitrogen-doped carbon) composite possesses ordered macro- and mesoporous nitrogen-doped carbon structures, where the ZnS quantum dots are embedded in. Due to their structural features, p-ZnS@CN showed a superior lithium storage performance in comparison with ZnS nanoparticles. The well-defined 3D interconnected hierarchical pore structure not only enhances the efficiency of lithium-ion diffusion, but also offers ample void space to buffer the volume expansion during lithiation. Given the diversity of crystalline organic hybrid metal thiocyanates, this work opens a new avenue of preparing 3D interconnected porous carbons-coupled metal-sulfide composites.

Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO2 Reduction of Yb(III) Complex with 4-Aacetylphenoxyacetic Acid and 1,10-Phenanthroline Ligands

A new nine-coordinated Yb(III) complex [YbL3(Phen)] (1) (HL = 2-(4-acetylphenoxy)acetic acid (APA), Phen = 1,10-phenanthroline) was synthesized with 2-(4-acetylphenoxy)acetic acid, YbCl3.6H2O, NaOH and 1,10-phenanthroline as materials. Complex (1) was characterized by IR and X-ray single-crystal diffraction analysis. The results show that the Yb(III) ion is nine-coordinated with seven carboxylate oxygen atoms from five different deprotonated APA ligands and two nitrogen atoms from one Phen ligand. Complex (1) forms a 3D supramolecular framework through the - stacking interactions between the Phen aromatic rings. The hirschfeld surface analysis of complex (1) was also calculated. The CO2 photoconversion activity of complex (1) has been performed under UV-vis light irradiation. The complex (1) shows good photocatalytic activity with the yield of CO is closed to 146 mmol/g after three hours of UV-vis light irradiation, the CO selectivity has reached to 97.9%. Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).