Search

Centrosymmetric homopolynuclear Cu(II) and Co(II) chelated complexes, [Cu2(L)(H2O)2] (1) and [Co4(L)(μ-OAc)2(CH3OH)4(OAC)2]⋅2CH2Cl2 (2), were synthesized using a new symmetrical methoxy-disubstituted bis(salamo)-type ligand, H4L, with Cu(II) and Co(II) salts in organic solvents. Complexes 1 and 2 were structurally characterized by single-crystal X-ray crystallography. The results indicated that 1 is a five-coordinate dinuclear structure containing Cu(II) and 2 is a tetranuclear Co(II) complex with two distinct six-coordinate environments. Furthermore, 1 and 2 pack into three-dimensional and two-dimensional extended networks, respectively. The UV–Vis spectra, IR spectra, and Hirshfeld surface analyses of the complexes were carried out to further characterize the coordination between H4L and the metal(II) ions. Fluorescence methods were used to interrogate the coordination, where changes in emission with varied amounts of ligand supported solution-phase coordination ratios of H4L with Cu(II) ion of 1:2 and with Co(II) ion of 1:4, respectively. [ABSTRACT FROM AUTHOR]

New di- and tetranuclear Cu(II) complexes, [Cu2(HL)Cl2(MeOH)]·MeOH·2CH2Cl2 (1) and [Cu4(L)2(MeOH)2](NO3)2·EtOH (2), have been synthesized from CuCl2·2H2O, Cu(NO3)2·3H2O and a symmetric 5-bromosalicylaldehyde-decorated bis(salamo)-like ligand (H3L, (1E,3E)-2-hydroxy-5-methylisophthalaldehyde O,O-di(2-((((E)-5-bromo-2-hydroxybenzylidene)amino)-oxy)ethyl)dioxime), and characterized by elemental analyses, IR and UV–vis spectra. Single crystal structure analyses showed a dinuclear Cu(II) structure for 1 and a tetranuclear Cu(II) structure for 2. In 1, two Cu(II) ions are on one side of the double N2O2 cavities, and the phenol proton in the other cavity is attached. In 2, four Cu(II) ions are located in four N2O2 cavities of two fully deprotonated L3− units, giving a centrosymmetric double helix structure. The Hirshfeld surfaces analyses, Interaction Region Indicator (IRI), and DFT computations of H3L, 1, and 2 were studied. In addition, the electrochemical and fluorescence properties of 1 and 2 were also investigated. [ABSTRACT FROM AUTHOR]

The coordination behaviors of asymmetric quinoline-decorated half-salamo-type ligand HL1 with Cu(NO3)2·3H2O and Cu(OAc)2·H2O were studied. Two Cu(II) complexes, [Cu(L1)(NO3)]·CH3CH2OH (1) and [Cu2(L2)2] (2), were isolated and characterized by X-ray crystallography, FTIR, UV–vis, and fluorescence spectroscopies. Structural analyses showed that 1 is a mononuclear species, whereas 2 is a binuclear entity. Spontaneous cleavage along the oxime N-O bond close to quinoline ring of the ligand HL1 occurred upon reaction with Cu(OAc)2·H2O, yielding an unexpected complex 2. Moreover, DFT theoretical calculations and Hirshfeld surfaces analyses of the ligand HL1 and its corresponding Cu(II) complexes were investigated in detail. [ABSTRACT FROM AUTHOR]

d-Block transition metal(II)-lanthanide(III) (3d-4f) hetero‐trinuclear [Cu(II)2Ln(III)] (Ln = La and Ce) complexes [Cu2La(L)(ƞ2-NO3)3(CH3OH)2]·2CH3OH (1) and [Cu2Ce(L)(ƞ2-NO3)3(CH3OH)2]·2CH3OH (2) are described, both of which are formed by a flexible symmetrical bis(salamo)-type ligand H4L. The two 3d-4f complexes have been synthesized and characterized by elemental analyses, IR spectra and UV–Vis spectroscopy. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction analyses. In 1 and 2, each Cu(II) ion (Cu1 or Cu2) is located in the N2O2 cavity of an (L)4− unit, while the apex is occupied by one oxygen atom of the coordinated methanol molecule, forming a penta-coordinated square pyramidal geometry. The lanthanide(III) (La or Ce) ion is located in the O6-donor coordination sphere of the completely deprotonated (L)4− unit and coordinated with the other six oxygen atoms of the three nitrate ligands to form a twelve-coordinated icosahedron. At the same time, the supramolecular structures are formed by intermolecular hydrogen bonding interactions and quantitatively determined by Hirshfeld surfaces analyses. Fluorescence properties and DFT calculations of 1 and 2 were also studied. [ABSTRACT FROM AUTHOR]

The potential health risk caused by long-term exposure to heavy metals in household dust is not only depended on their total content, but also bioaccessibility. In this study, twenty-one dust samples were collected from residential buildings, schools, and laboratories in 14 provincial-capital/industrial cities of China, aiming to evaluate the total contents, fractionation, bioaccessibility and health risks of nine heavy metals (As, Cd, Cr, Ni, Pb, Mn, Zn, Fe, and Cu). Results showed that the highest levels of Cd, Cr, Ni and Zn were found in laboratory dust, As, Pb and Mn in school dust, and Fe and Cu in residential dust, indicating different source profiles of the heavy metals. The mean bioaccessibility of the heavy metals across all samples as evaluated using SBRC (Solubility Bioavailability Research Consortium), IVG (In Vitro Gastrointestinal), and PBET (Physiologically Based Extraction Test) assays was 58.4%, 32.4% and 17.2% in gastric phase (GP), and 24.9%, 21.9% and 9.39% in intestinal phase (IP), respectively. Cadmium had the highest content in the fractions of E1+C2 (43.7%), as determined by sequential extraction, and Pb, Mn, and Zn had a higher content in E1+C2+F3 (64.2%, 67.2%, 78.8%), resulting in a higher bioaccessibility of these heavy metals than others. Moreover, the bioaccessibility of most heavy metals was inversely related to dust pH (R = −0.18 in GP; −0.18 in IP; P < 0.01) and particle size, while a positive correlation was observed with total organic carbon (R = 0.40 in GP; 0.38 in IP; P < 0.01). The exposure risk calculated by the highest bioaccessibility was generally lower than that calculated by the total content. However, Pb in one school dust sample had an unacceptable carcinogenic risk (adult risk = 1.19 × 10−4; child risk = 1.08 × 10−4). This study suggests that bioaccessibility of heavy metals in household dust is likely related to geochemical fractions and physical/chemical properties. Further research is needed to explore the sources of bioaccessible heavy metals in household dust. [Display omitted] • Bioaccessibility of nine metals in 21 household dusts from 14 cities were studied. • Bioaccessibility showed a trend of SBRC > IVG > PBET. • Metal bioaccessibility was positively correlated with dust TOC and E1+C2 fractions. • Metal bioaccessibility was inversely related to dust pH and particle size. • Bioaccessibility-based health risks of heavy metal were assessed and more accurate. [ABSTRACT FROM AUTHOR]

• A salamo-type probe l-Cu2+ containing 1,8-naphthalimide fluorophore was synthesized firstly. • The probe l-Cu2+ can specifically detect S2- further validated through ESP analysis. • Good results in test strip, actual water samples and antibacterial activity were achieved. A novel salamo-based fluorescent chemical sensor l-Cu2+ was designed and prepared via the reaction of H 2 L and Cu(OAc) 2 ·H 2 O. The whole research has found that Cu(II) atom in the complex crystal are located in the N 2 O 2 cavity of H 2 L, forming a four-coordination system. Hirshfeld surface analysis confirmed the presence of hydrogen bonding and π···π stacking interactions. As a probe molecule, l-Cu2+ can selectively and sensitively detect S2- without interference from other ions, and can be effectively used within the biological pH range. In addition, DFT theoretical calculations and molecular electrostatic potential analysis (ESP) were used to investigate the electron cloud density and positive and negative electrostatic potentials inside the probe, as well as the mechanism for identifying sulfur ions. Finally, the probe l-Cu2+ has shown good practical application effects and can recognize S2− in three different water samples. It can also be used as a qualitative detection strip. l-Cu2+ complex possesses excellent application prospect in bacteriostasis. [Display omitted] [ABSTRACT FROM AUTHOR]

• A quinoline-including half-salamo like N 3 O-donor ligand was synthesized. • Differently structural Cu(II) and Ni(II) complexes were synthesized and structurally characterized. • The intermolecular interactions were quantitatively analyzed by hirshfeld surfaces and 2D fingerprint plots. A half-salamo like N 3 O-donor ligand HL was synthesized and used for the construction of Cu(II) and Ni(II) complexes, namely as [Cu(L)(NO 3)] (1) & [Ni 2 (L) 2 (NO 3) 2 ]·2H 2 O (2). The constructed complexes were structurally characterized by X‐ray crystallography technique. The results revealed that the complex 1 is the most common mononuclear species, in which Cu(II) ion is penta-coordinate with twisted square pyramid configuration. Unlike complex 1, the central Ni(II) ions of dinuclear complex 2 are hexa-coordinate possessing slightly distorted octahedron. The final supramolecular structures of the two complexes are stabilized and expanded by noncovalent interactions. In addition, spectral characteristics of the title complexes were examined. The frontier molecular orbitals as well as energy gaps of the complexes were explored by density functional theory calculation. The primary aspects of the ultraviolet absorption spectra were interpreted using time-dependent density functional theory computation. Thorough analysis of the Hirshfeld surfaces quantifies the interactions involved in the crystal structures of the Cu(II) and Ni(II) complexes. Two differently structural metal(II) complexes [Cu(L)(NO 3)] (1) and [Ni 2 (L) 2 (NO 3) 2 ]·2H 2 O (2) containing a half-salamo like N 3 O-donor ligand were successfully synthesized and characterized. The spectral properties of the two complexes were studied. Moreover, the frontier molecular orbitals as well as energy gaps of the complexes were explored by DFT calculation. The Hirshfeld surfaces analyses and 2D fingerprint plots were performed to quantify the interactions involved in the crystal structures of the two complexes. [Display omitted] [ABSTRACT FROM AUTHOR]

• Two different Cu(II) salamo-salen-salamo-hybrid complexes were synthesized • Salen on the hybrid ligand has stronger coordination ability than salamo moiety • Salamo chain orientation and structure of the complexes vary due to solvent effect • H 4 L and its complexes were characterized by MESP, IRI analyzes and DFT calculation Based on the condensation reaction of a containg-formyl asymmetric salamo-based ligand with ethylenediamine, a salamo-salen-salamo-hybrid multi-compartment ligand possessing both salen and salamo structural moieties was prepared, and its different types (Cu(II): H 2 L)2−) of copper(II) complexes, confirmed as [Cu(H 2 L)] 2 ·4EtOH (1) and [Cu 2 (H 2 L) 2 ]·2MeOH·(Me) 2 CO (2), have been synthesized and elucidated structurally. In the complexes, Cu(II) ion is sited at the salen's N 2 O 2 cavity, while the salamo structural moieties do not participate in coordination. This coordination characteristic indicates that the coordination ability of salen and salamo structural moieties in salamo-salen-salamo-hybrid ligand varies, with salen having relatively stronger coordination ability, which may be due to the incorporation of more electronegative multiple O atoms on C=N bonds, resulting in a decrease in the electron cloud density on the N atoms of the multi-oxime groups and a decrease in the coordination ability. Thus, Salen structural moiety on the hybrid ligand has stronger coordination ability than salamo structural moieties. In addition, due to the solvent effect, the extension direction of the single salamo long chain is different, and the configurations of the complexes are also different. Through X-ray diffraction analysis and DFT theoretical computations of the ligand and the complexes, the weak intramolecular and intermolecular interactions of the complexes, as well as the intermolecular C-H···π & π···π interactions of the complexes, were discussed. The ligand and the copper(II) complexes were analyzed for their MESP, as well as to show the mobile regions of the molecules in the complex molecules. Due to the solvent effect, the spatial orientation of the long chain of salamo has undergone significant changes, changing the region where the complex molecules move in a specific space. [Display omitted] [ABSTRACT FROM AUTHOR]

A formyl-coordinated phenoxo-bridged homopolynuclear dimeric Cu(II) complex of a salamo-like N 2 O 3 -donor ligand, [(L) 2 Cu 3 (MeOH) 2 ](ClO 4) 2 , has been synthesized and characterized structurally. The weak interactions of the Cu(II) complex were studied via MEPs, IRI and Hirshfeld surfaces analyses, and the energy gaps and electronic properties of H2L and the Cu(II) complex were investigated through DFT & TD-DFT calculations. [Display omitted] • A rare trinuclear Cu(II) complex was synthesized and characterized structurally. • Both phenoxy and formyl oxygen atoms participate in coordination. • The weak interactions were studied via MEPs, IRI and Hirshfeld surfaces analyses. • The energy gaps and electronic properties were investigated through DFT & TD-DFT calculations. A formyl-included salamo-based N 2 O 3 -donor ligand (H 2 L) was synthesized, and has two cavities of N 2 O 2 and O 3. Coordination reactivity of the ligand H 2 L toward Cu(II) atoms can result in an unprecedented centrosymmetric sandwich-like homotrinuclear Cu(II) complex, [(L) 2 Cu 3 (MeOH) 2 ](ClO 4) 2 , here Cu1 lies in the N 2 O 2 positions, Cu2 is surrounded at the O 6 coordination sphere and bridged via two metalated [(L)Cu(MeOH)] units, and coordinates further with two oxygen atoms of formyl groups of another two ligand (L)2- moieties. Finally, the dimeric structure's complex was elucidated by elemental analyses and infrared spectroscopy, and fluorescence behaviors of the formyl-included ligand and the title complex were investigated. The weak interactions of the title complex were studied via MEPs, IRI and Hirshfeld surfaces analyses. Finally, the energy gaps and electronic properties of H 2 L and the title complex were investigated through DFT & TD-DFT calculations. [ABSTRACT FROM AUTHOR]

• Binuclear and novel tetranuclear Cu(II) were synthesized and characterized. • The geometries of Cu(II) atoms in complexes 1 and 2 are distinctly different. • The 3-hydroxy coordination easily forms a polynuclear complex. • Different counterions and solvents can give rise to various complexes. • Complexes 1 and 2 show some degree of fluorescence quenching. In this work, a linear acyclic oligo(N,O-donor) salamo-based chelate ligand H 4 L containing both dioxime and Schiff base functionalities was synthesized. Its various bi-nuclear and tetra-nuclear complexes, [Cu 2 (HL)(μ -OAc)]·CH 3 OH (1) and [Cu 4 (HL) 2 (EtOH)](ClO 4) 2 ·2EtOH (2) were self-assembled via the ligand H 4 L with stoichiometric quantities of Cu(OAc) 2 ·H 2 O/Cu(ClO 4) 2 ·6H 2 O in methanol/ethanol, respectively. The bi-nuclear complex 1 consists of a partly deprotonated (HL)3− anion, two Cu(II) atoms, one μ -OAc− counterion. Each Cu(II) atom center is surrounded by a tetragonal cone geometry. However, complex 2 containing four Cu(II) ions, two partially deprotonated (HL)3− anions, and a ligated ethanol molecule, which forms tetranuclear complex 2 containing four and five-coordinated geometries. The structure of complex 2 acquired is unique as shown herein, the different nucleation numbers and geometrical configurations of the resulting crystal structures may be due to the different anions and solvents used in the synthesis process. The binding ratios of the oligo(N,O-donor) ligand to Cu(II) ions were confirmed by UV titration experiments, two of which are consistented with the single-crystal structures. Finally, MEPs, IRI, Hirshfeld surfaces, and intermolecular interactions and reactive sites were analyzed further, the fluorescent properties were explored. Bi- and tetra-nuclear Cu(II) salamo-based complexes, [Cu 2 (HL)(μ -OAc)]·CH 3 OH (1) and [Cu 4 (HL) 2 (EtOH)](ClO 4) 2 ·2EtOH (2) were synthesized and structurally characterized. Complexes 1 and 2 possess four- and five-coordinated geometries, The intermolecular interactions of Cu(II) complexes 1 and 2 were elucidated, which are consistent with the crystal structures. The fluorescence properties of H 4 L and its Cu(II) complexes were investigated. [Display omitted] [ABSTRACT FROM AUTHOR]

• A novel three-bridged trinuclear [{Co 3 (L) 2 (µ 3 OAc) 2 } 2 ] complex with acetate was constructed. • Fluorescence properties of the ligand and its complexes were studied. • A series of theoretical calculations of the ligand and its complexes were investigated. • The softness of the complexes was proposed and energy gaps were analyzed by DFT calculation. • Quantitative analyses of intermolecular interactions in the crystalline structures were performed by Hirshfeld surfaces analysis. A more flexible 3-methoxysalamo-like ligand H 2 L and its dinuclear Cu(II) complex [Cu 2 (L)(NO 3) 2 ] (1) and novel trinuclear Co(II) complex [{Co 3 (L) 2 (µ 3 OAc) 2 } 2 ]⋅9CH 2 Cl 2 (2) were synthesized. The self-assembly reaction was driven by the unique N , O-donor coordination environments. Single crystal X-ray diffraction analysis showed that two Cu(II) atoms occupy the N 2 O 2 and O 4 cavities of the ligand (L)2− unit in complex 1 , respectively, and two oxygen atoms on the two mono-dentate nitrate groups have also participated in the coordination for the charge balance of complex 1. The stretching of chemical bonds of complex 1 can be perfectly explained by the Jahn-Teller effect. The novel salamo-based Co(II) complex 2 containing µ 3 OAc− coordination mode was discovered for the first time. The trinuclear Co(II) complex embodies the advantage of the salamo-based ligand, which has a good flexible form. The binding ratio of the ligand to the Co(II) center was verified by a UV–Vis titration experiment, which is consistent with the single crystal X-ray diffraction result. The energy gaps between the ligand and complexes 1 and 2 were obtained by DFT calculations, and a new theory-softness was proposed. The degree of softness affected the shapes of the complexes. Hirshfeld analysis, IRI, and electrostatic potential proved the existence of hydrogen bond, π···π, C H···π interactions, and van der Waals force. These weak interaction forces affected the structures of the complexes. Finally, the fluorescence properties of the ligand and its complexes were studied. [ABSTRACT FROM AUTHOR]

• An unexpected mono-nuclear Cu(II) complex was successfully prepared. • The complex is formed by the reaction of Cu(II) acetate with H 2 L1, not by the H 3 L. • DFT, ESP and Hirshfeld surfaces analyses of the Cu(II) complex were investigated. An unexpected mono-nuclear Cu(II) complex [Cu(L1)] was successfully prepared by a bis(salamo)-type ligand H 3 L and Cu(OAc) 2 ·H 2 O in ethanol/acetone mixed solvent, and its structure and properties were analyzed. The crystal structure analysis showed that the Cu(II) complex is obtained by the reaction of copper(II) acetate with a new single salamo-type ligand H 2 L1, not obtained from the original ligand H 3 L. The molecular front orbitals HOMO and LUMO of the ligand H 3 L and the Cu(II) complex were analyzed by quantum chemical calculations, and the results showed that the energy gap of the Cu(II) complex is reduced due to the combination of orbitals compared to the ligand. The theoretical reaction sites of the ligand H 3 L with the Cu(II) were analyzed by ESP studies, and the results showed that the crystal structure of the Cu(II) complex is consistent with the theoretical predictions. Hirshfeld surfaces analyses confirmed the rich and diverse interactions present in the Cu(II) complex, which is essential for the stability of the molecules. [Display omitted] The unexpected Cu(II) complex [Cu(L1)] was successfully prepared by a bis(salamo)-type ligand H 3 L, and its structure and properties were analyzed. Unexpectedly, the obtained complex was not formed by the original ligand, but the new ligand formed, H 2 L1, reacted with copper acetate to obtain a mononuclear copper complex due to the catalytic effect of copper acetate on the ligand at N O bond in the oxime group leading to the breakage of the ligand. [ABSTRACT FROM AUTHOR]

• A novel tetranuclear Cu(II) salamo-like complex has been synthesized and characterized structurally. • Different modes of the Cu(II) complex were obtained by changing the reaction ratio between H4L and copper(II) salts. • The four Cu(II) atoms possess respectively four- and five-coordinated modes. • A series of theoretical calculations and fluorescence properties of H4L and its Cu(Ⅱ) complex were investigated. A novel tetra-nuclear Cu(II) salamo-like complex containing four- and five-coordinated Cu(II) atoms, [Cu 4 (L) 2 (MeOH) 2 ]·2MeOH was synthesized and characterized structurally. The single crystal X-ray diffraction analysis indicated the Cu(II) complex is a triclinic system, including four Cu(II) atoms and two completely deprotonated ligand (L)4− units, forming an asymmetric geometric structure. Specifically, Cu2 and Cu4 atoms are located in the N 2 O 2 cavities of two different ligand (L)4− units, respectively, and coordinate with one methanol molecule in the axial position to form five-coordinated tetragonal pyramid geometries. Meanwhile, Cu1 and Cu3 atoms respectively coordinate with four phenoxy atoms in the two ligand (L)4− units to form slightly distorted planar quadrilateral geometries with four coordination. The spectral properties of the ligand H 4 L and its Cu(II) complex were further analyzed by IR, UV–vis absorption spectra and fluorescence spectra. DFT calculation results showed that the Cu(II) complex has low optical reaction activity. In addition, the electrophilic and nucleophilic sites favorable for the formation of hydrogen bonds were found through molecular electrostatic potential analysis. Hirshfeld surface analysis identified the interactions in the crystal structure. In the Cu(II) complex, H···H/H···H interaction is dominant, indicating that there are a large number of hydrogen bonds in the complex. IRI analysis revealed that there are weak hydrogen bond interactions, all of which make the Cu(II) complex more stable. [ABSTRACT FROM AUTHOR]

• The first salamo-type mixed-ligand metal(II) polymer was synthesized and characterized structurally. • The interaction forces existing within the polymer molecules were investigated by relevant theoretical calculations. • The antimicrobial activities of the two ligands and their polymer were investigated. In this work, a copper(II) coordination polymer [Cu 2 (L1)(L2)(NO 3)] n ·nCH 3 OH (Cu(II)-CP) with different structures of mixed salamo-type ligands was constructed for the first time. Single crystal X-ray diffraction analysis showed that the Cu(II)-CP asymmetric unit consists of two copper(II) atoms, fully deprotonated (L1)−, (L2)2− ligand units, one NO 3 − anion and one molecule of crystallized methanol. The two metallized ligand units are bridged by two oxygen atoms of NO 3 − to form unique mixed-ligand copper(II) coordination polymer. In addition, the six coordination atoms around the two Cu(II) atoms are all arranged in a distorted octahedral geometry. In the molecular structure of Cu(II)-CP , neighbouring molecules interact through intermolecular hydrogen bonds to form a two-dimensional supramolecular structure. Intermolecular interactions and molecular stability were further investigated by Hirshfeld surface analysis and other theoretical calculations. Finally, the antimicrobial activities of both ligands and Cu(II)-CP were investigated and found to exhibit excellent antibacterial activities. [Display omitted] A Cu(II) coordination polymer [Cu 2 (L1)(L2)(NO 3)] n ·nCH 3 OH with salamo-type mixed ligands was synthesized for the first time. The structure of the polymer was characterized and the intramolecular forces were studied through theoretical calculations. In addition, the antimicrobial activities of the two ligands and their polymer were investigated. [ABSTRACT FROM AUTHOR]

• The compound HL1 can spontaneously catalyze during coordination self-assembly. • Co(II) ions and tri-bridged o atoms in complex 2 form a novel cuboidal structure. • Dimer 1 and cluster 2 exhibit efficient dye degradations. The design and synthesis of structurally rich chemical materials for detection, analysis, and purification is challenging. In this regard, two functional 3d metal(II) complexes bearing the half-salamo-type compound HL1 (2-[ O -(1- ethyloxyamide)]oxime-3‑methoxy-5‑bromo-phenol) have been synthesized, namely: [Cu 2 (L2) 2 ]·2CH 3 CN (1) and [Co 4 (L2) 4 (CH 3 CH 2 OH) 4 ] (2). Complexes 1 and 2 were fully characterized by single-crystal X-ray diffraction, elemental analysis, and FT-IR and UV–Vis spectroscopy. The crystal structure analysis revealed that complex 1 is a centrosymmetric oxo-bridged Cu(II) dimer formed by connecting two metalloligand [Cu(L2)] units. The coordination self-assembly in complex 2 was triggered to obtain a unique tetranuclear Co(II) cuboidal cluster of S 4 symmetry based on a [Co(L2)] metalloligand unit. The experimental results showed that HL1 spontaneously catalyzes the formation of new compound H 2 L2 during the formation of complexes 1 and 2. The photocatalytic degradation properties of dimer 1 and cluster 2 were investigated for several dye pollutants: methyl orange (MO), methylene blue (MB), and Rhodamine B (RhB) under H 2 O 2 initiation. Additionally, DFT calculations were performed to further understand the structure-property relationship between the electron characteristics and the photocatalytic degradation behaviors. Oxo-bridged half-salamo-type Cu(II) dimer and tetranuclear Co(II) cuboidal cluster have been successfully developed as a photocatalytic platform for efficient degradation of MB, MO, and RhB dyes. [Display omitted] [ABSTRACT FROM AUTHOR]

• Heterobimetalic [Cu(II)2Ln(III)] (Ln = La and Ce) complexes were synthesized and characterized structurally. • It can be seen from complex 2 that the coordination ability of nitrate is stronger than that of acetic acid. • Hirshfeld surface analyses, DFT calculations and luminescences of the complexes 1 and 2 were investigated. Two heterobimetallic [Cu(II) 2 Ln(III)] (Ln = La and Ce) complexes composed of flexible bis(salamo)‐type ligand H 4 L with Cu(II) and Ln(III) atoms, [Cu 2 La(L)(ƞ 2-NO 3) 3 ]·EtOH (1) and [Cu 2 Ce(L)(ƞ 2-NO 3) 3 ]·EtOH (2) have been successfully synthesized, and characterized by IR spectra, elemental analyses, UV–Vis spectroscopy, the crystal structures of the complexes 1 and 2 were determined by single-crystal X-ray diffraction analyses. Each Cu(II) atom of the complexes 1 and 2 is located in the N 2 O 2 -donor of the completely deprotonated (L)4− unit, so that the two Cu(II) atoms have tetra-coordinated slightly distorted square planar geometries, while the Ln(III) (La or Ce) atom is located in the O 5 cavity of the ligand (L)4− unit. At the same time, there are six oxygen atoms from three bidentate nitrate groups coordinated with the Ln(III) (La or Ce) atom, resulting in the formation of an eleven-coordinated augmented sphenocorona J87. In addition, DFT calculations and Hirshfeld surfaces analyses are performed and fluorescence properties are evaluated. [Display omitted] Two heterobimetalic [Cu(II)2Ln(III)] (Ln = La and Ce) complexes composed of a flexible bis(salamo)‐type ligand H4L with Cu(II) and lanthanide(III) atoms, [Cu 2 La(L)(ƞ2-NO 3) 3 ]·EtOH (1) and [Cu 2 Ce(L)(ƞ2-NO 3) 3 ]·EtOH (2) have been successfully synthesized. The central lanthanide(III) atom forms eleven-coordinated augmented sphenocorona J87. At the same time, DFT calculations are performed and fluorescence properties are evaluated. [ABSTRACT FROM AUTHOR]

• Shrimp shell (SS) can be used as substrate for electricity generation of MFCs. • The operation time and Cu removal capacity of the MFC-SS were longer and higher. • The higher the SS concentration, the better performance of the Cu removal. High-content solid waste (HCSWs) contains numerous polysaccharides and is widely recognized as an energy-generating substance. However, detailed studies on the use of HCSWs as substrates in microbial fuel cells (MFCs) to generate electricity and remove heavy metals from wastewater are scarce. In this study, the effects of shrimp shell (SS) and sodium acetate (SA), which are complex and simple substrates, respectively, as anodic carbon sources on the electricity generation performance of dual-chamber MFCs and the removal of Cu at the cathode were investigated. The structural characteristics of the anodic microbial communities of the MFCs were analyzed in terms of substrate type and concentration. The results demonstrated that the maximum voltage (206 mV) and maximum power density (28.82 mW/m2) of the MFC-SA were higher than those of the MFC-SS groups. The operating time and maximum power density increased with increasing SS concentration, and the maximum power density reached 24.75 mW/m2 at an SS concentration of 16 g/L. The Cu2+ ions in the catholyte were primarily reduced to elemental Cu and small amounts of Cu 2 O or CuO. The higher the concentration of SS, the higher the Cu removal rate, the greater the total amount of Cu removed, and the higher the MFC removal capacity. Pseudomonas was the only electroactive microorganism in the raw sludge, whereas Geobacter, Corynebacterium, Clostridium, Desulfovibrio , and Desulfosporosinus were detected in the MFCs at the end of the experiment. The relative abundance of the electroactive microorganisms increased from 19.4% to 36.0% as the SS concentration increased from 2 to 16 g/L. These results suggest that SS can be used as substrate for HCSW degradation to provide the energy required for heavy-metal reduction. [ABSTRACT FROM AUTHOR]

Two penta-coordinated multinuclear copper(II) complexes, [Cu 2 (L)(µ -OAc)]·MeOH (1) and [Cu 4 (L) 2 Cl 2 ]·EtOH·CH 2 Cl 2 (2) have been synthesized and characterized structurally. IR spectra, UV–vis spectra and fluorescence properties of complexes 1 and 2 have been investigated. [Display omitted] • Two copper(II) complexes were synthesized and characterized structurally. • All of Cu(II) atoms have the geometries of almost perfect tetragonal pyramid. • Fluorescence properties of complexes 1 and 2 have been investigated. With the reactions of a single-armed salamo-based ligand H 3 L and two kinds of copper(II) salts (Cu(OAc) 2 ·H 2 O or CuCl 2 ·2H 2 O) in mixed organic solvents, respectively, two penta-coordinated Cu(II) complexes [Cu 2 (L)(µ -OAc)]·MeOH (1) and [Cu 4 (L) 2 Cl 2 ]·EtOH·CH 2 Cl 2 (2) have been successfully constructed. The precise structures of the two Cu(II) complexes obtained by solvent evaporation method are measured by single crystal X-ray diffraction analyses. The di-nuclear complex 1 crystallizes in triclinic space group P -1, where the main structure is compose of two Cu(II) atoms, one completely deprotonated ligand (L)3− unit, one bridged μ -OAc− counter-anion and one crystallized methanol molecule. The tetra-nuclear complex 2 with an inversion center crystallizes in the same space group as 1 and contains four Cu(II) atoms, two fully deprotonated salamo-based ligand (L)3− units, two bridged Cl− counter-anions, one crystallized dichloromethane and one ethanol molecules. Compared to preceding complexes based on other single-armed salamo-based ligands, the structure of complex 2 reported in this work is unique and has never been found in previous literatures. All of Cu(II) atoms in complexes 1 and 2 are penta-coordinated with the geometries of distorted tetragonal pyramid, and the τ 5 value of all Cu(II) atoms have been calculated and all results are less than 0.5. Hirshfeld surfaces analyses of complexes 1 and 2 have been established to explain the interactions of crystal structures, and the corresponding two-dimensional (2D) fingerprint plots have been carried out to quantify the intermolecular interactions. In addition, fluorescence properties of complexes 1 and 2 have been investigated. [ABSTRACT FROM AUTHOR]

• The first 3d-3d′ heterobimetallic [Cu(II) 2 Mn(II)] bis(salamo)-based complex was synthesized and characterized structurally. • The different natures of the N 2 O 2 and O 6 sites of H 4 L lead to the site‐selective introduction of two various metal(II) atoms. • Unusual fluorescence behavior of the [Cu(II) 2 Mn(II)] complex was reported. The first 3d-3d′ heterobimetallic [Cu(II) 2 Mn(II)] complex, [Cu 2 Mn(L)(µ 2 -NO 3) 2 ] was reported, and formed by an acyclic tricompartmental bis(salamo)-based ligand H 4 L and different metal salts. Its structure was characterized by physicochemical and spectroscopic methods. The ligand H 4 L has two identical N 2 O 2 sites and one O 6 site separated by phenoxy groups. Two penta-coordinate Cu(II) atoms and one octa-coordinated Mn(II) atom are located respectively in these two different coordination environments. Through the analysis of the Hirshfeld surfaces of the [Cu(II) 2 Mn(II)] complex, the intermolecular interactions involved in the crystal structure can be shown, and the corresponding quantitative information is given by fingerprint. The [Cu(II) 2 Mn(II)] complex units are combined by intermolecular C-H•••O hydrogen bonds to form a two-dimensional supramolecular structure. Unusual fluorescence behavior of the [Cu(II) 2 Mn(II)] complex was further studied. [Display omitted] [ABSTRACT FROM AUTHOR]