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Tetranitroethane (TNE), an energetic compound with high-nitrogen (N%, 26.7%) and oxygen (O%, 60.9%) content, is deprotonated by alkali and alkaline earth metal bases to form the corresponding metal salts of TNE which are characterized by FT-IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. All the prepared energetic metal salts show excellent thermal stabilities, and the decomposition temperatures of EP-3, EP-4, and EP-5 are higher than 250 °C, due to the numerous coordination bonds of the complexes. Furthermore, the energy of formation of the nitrogen-rich salts were calculated utilizing heat of combustion. The detonation performances were calculated with the EXPLO5 software, and the impact and friction sensitivities were determined. EP-7 shows excellent energy performance (P = 30.0 GPa, VD = 8436 m s−1). EP-3, EP-4, EP-5, and EP-8 are more sensitive to mechanical stimulation. These alkali and alkaline earth metal salts of TNE show good monochromaticity by atomic emission spectroscopy (visible light), and may be used as potential flame colorants in pyrotechnics. [ABSTRACT FROM AUTHOR]

Two new coordination polymers (CPs), [Zn(HL)2(bipy)]n·2nCH3OH (Zn(II)-CP) and [Cd(HL)2(bipy)]n (Cd(II)-CP), were synthesized from a nonsymmetric salamo-based ligand, 4-chloro-4′-bromo-6-bromo-6′-tert-butyl-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol (H2L). Single crystal X-ray diffraction analysis showed that both Zn(II) and Cd(II) coordinate with the two semi-deprotonated ligands (HL)− and two 4,4′-bipyridine (bipy) auxiliary ligands, yielding slightly twisted octahedral configurations. The two one-dimensional (1-D) chain polymers are further connected by hydrogen bonds (H-bonds) to form interesting 3-D supramolecular structures. These intermolecular interactions and molecular stability were investigated by Hirshfeld surface analyses and Density Functional Theory (DFT) calculations. Luminescent studies show that these two CPs have potential application as light emitting devices. [ABSTRACT FROM AUTHOR]

Guided by synthetic chemistry, coordination chemistry and crystallization chemistry, a novel synthesis and crystallization strategy for laser complex energetic materials has been established in this study. In this study, a method with milder reaction conditions was adopted to design the steps and successfully synthesize urazine (H2ur). At the same time, using H2ur as the ligand, the "acid-controlled dissolution-crystallization" method was used to successfully prepare the crystalline coordination polymer Ag(H2ur)NO3 (5), and its 1D structure was confirmed by X-ray single crystal diffraction. The physicochemical property evaluation revealed that 5 has the best performance: insensitive to light, noncorrosive properties to metal shells, excellent tolerance to moisture, good thermal stability, and insensitive to mechanical stimulation. Theoretical calculations show that the compound has acceptable detonation properties (D = 7.6 km s−1, P = 31.83 GPa). In addition, hot-needle experiments show that 5 has a good DDT effect. More importantly, it has great potential for application in laser energetic materials (τ = 300 ms, E = 800 mJ). [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]

Two novel homomultinuclear complexes [Co6(L)2(μ‐OAc)4]·2CHCl3·CH3COCH3 (1) and [Ni2(L)(H2O)2(Py)2]·2CHCl3 (2) with a newly designed rigid bis(salamo)‐type tetraoxime ligand (H4L) were synthesized and characterized by elemental analyses, Fourier transform infrared (FT‐IR) spectra, UV–Vis absorption spectra, and X‐ray single‐crystal diffractions. Complex 1 is a novel triple‐decker symmetrical six‐core cluster structure with twofold axis and inversion center. The Co(II) atoms were sandwiched between the bis(salamo)‐type ligands and possess two different geometries of distorted tetragonal pyramid and octahedron, respectively. Complex 2 possesses a dinuclear structure and the Ni(II) atoms are located in the N2O2 cavities of the ligand, and axial coordination atoms come from the coordinated water and pyridine molecules. Both Ni(II) atoms adopt distorted octahedral geometries. The interactions were quantitatively determined by Hirshfeld surfaces analyses of complexes 1 and 2. The coordination ratios were determined by studying the fluorescence properties of complexes 1 and 2. The results of fluorescence titration experiment show that the metals to ligand binding ratios are 6:2 and 2:1 for complexes 1 and 2, respectively. [ABSTRACT FROM AUTHOR]

Two dinuclear Ni (II) and Zn (II) salamo‐type complexes, [Ni2(L)(μ‐OAc)(MeOH)]·2CHCl3 (1) and [{Zn2(L)(μ‐OMe)}3]·3CHCl3·MeOH (2), have been successfully synthesized by wet‐chemical method and characterized by elemental analyses, IR spectra, UV–Vis spectra and single crystal X‐ray diffraction. Complex 1 consists of two closely related dinuclear units 1A and 1B, and complex 2 consists of three closely related dinuclear units 2A, 2B and 2C. The five units are unique example of crystallographically independent but chemically identical molecules. The Ni (II) atoms of complex 1 are located in the N2O4 coordination cavities, possessing six‐coordinated distorted octahedral geometries, but all Zn (II) atoms in complex 2 are located in the N2O3 coordination cavities, possessing five‐coordinated distorted square‐pyramid and triangular bipyramid geometries, the geometries about the Zn (II) atoms (Zn3 and Zn6) that obtain in 2B and 2C where τ5 is very close to 0.500, which is τ5Zn3 = 0.5006 and τ5Zn6 = 0.4941, respectively. The interactions were quantitatively determined by Hirshfeld surfaces analyses. Significantly, fluorescence properties were also investigated. [ABSTRACT FROM AUTHOR]

Using symmetrical bis (salamo)‐type tetraoxime ligand H3L and Cu (ClO4)2·6H2O in different solvent systems, two unusual homomultinuclear Cu (II) complexes, [Cu4(L)2(CH3CH2OH)2](ClO4)2·2H2O (1) and [Cu2(L)]n (ClO4)n·nCH3CN (2), were synthesized and characterized by single‐crystal X‐ray diffraction analyses, elemental analyses, infrared (IR), ultraviolet–visible (UV–Vis) spectroscopy, Hirshfeld surfaces analyses, and density functional theory (DFT) calculations. Complex 1 includes [Cu4(L)2(CH3CH2OH)2]2+ ion, two ClO4− counter anions, two coordinated ethanol molecules and two aquatic dissociative molecules, the two deprotonated ligand (L)3− units package around four Cu (II) ions yield a centrosymmetric helical molecules with a charged linear folding center, while complex 2 forms a 1‐D linear topology structure and is only the substitution of chloroform in the solvent system of complex 1 with acetonitrile. Coordination mode of complex 2 is widely different from that of complex 1. In the Cu (II) ions of complex 1, there are two coordination modes of Cu (II) ions, the hexa‐coordinated distorted octahedral structure and the penta‐coordinated distorted tetragonal pyramid structure, but complex 2 only has almost perfect tetragonal pyramid geometry. Fluorescence properties of H3L and its complexes 1 and 2 have also been explored. [ABSTRACT FROM AUTHOR]

• A nonsymmetric salamo-type ligand H 2 L with an exposed aldehyde was synthesized. • Novel Zn(II) complex and Ni(II) CP were synthesized and characterized. • The theoretical calculations to verify the stability and electroneutrality of the Zn(II) complex and Ni(II) CP. In the first step, we synthesized a nonsymmetric salamo-like ligand, H 2 L, featuring 4-hydroxyisophthalaldehyde and 6‑methoxy-2-[ O -(1-ethoxyamide)]oxime phenol. In the subsequent phase, Zn(II) and Ni(II) complexes, namely [Zn 2 (L) 2 ]·2CH 3 CN·CH 3 OH and [Ni(L)(H 2 O)] n ·nCH 3 COCH 3 , were obtained by treating H 2 L with Zn(II) and Ni(II) ions via a solvent volatilization method. Structural characterizations were carried out using various techniques, including 1H NMR, MS, and X-ray diffraction analysis. Where the phenolic oxygen atoms (O4, O8) bridging two metal atoms (Zn1, Zn2), both five-coordinated Zn(II) atoms are in twisted triangular bipyramidal geometrical configurations, while the Ni(II) atom exhibits a six-coordinated octahedral geometric configuration, the formyl group only participates in the coordination of Ni(II) atom. The existence of multiple interactions, as well as charge distributions between the complexes or CPs (coordination polymers), has also been demonstrated through theoretical calculations IRI (Interaction region indicator), MESP (Molecular electrostatic potential) and Hirshfeld, etc. Fluorescence experiment revealed a significant enhancement in fluorescence intensity upon addition of Zn(OAc) 2 ·2H 2 O, while the fluorescence intensity was quenched upon addition of Ni(NO 3) 2 ·6H 2 O. [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 novel Salamo-Salen-Salamo hybrid ligand H 4 L was explored. • Mononuclear Salamo-Salen-Salamo-Ni(II) complex has been synthesized and characterized structurally. • A series of theoretical calculations of the Ni(II) complex were performed. The Salen compound is a typical Schiff base ligand, and by combining one Salen-structure unit with two Salamo-structure units, a novel hybrid Salamo-Salen-Salamo-type ligand H 4 L was synthesized. The synthesis of corresponding complexes based on the hybrid ligand was studied. Ni(II) ion participates in coordination and synthesizes a hybrid Salamo-Salen-Salamo-type mononuclear complex [Ni(LH 2)]. X-ray single crystal diffraction analysis showed that Ni(II) ion has coordinated with Salen N 2 O 2 structure, forming a planar geometry with tetracoordination. The Salamo structure units are not involved in coordination, and two Salamo long chains are spatially close to each other and there are N, O atoms that are easy to coordinate with metals, forming a potential coordination environment. The spectral properties of the complex was further discussed by IR and UV-vis spectroscopy, and the binding ratio of the ligand H 4 L to Ni(II) ion in solution was verified by UV-vis titration spectroscopy. Through the structural optimization of the ligand and single-point energy calculation of the complex, the HOMO-LUMO gaps of the ligand and the complex were analyzed to determine the softness of the ligand and the complex. TD-DFT analysis of the ligand and its complex was found to be consistent with experimental results, and the energy level transition sources of the main absorption peaks and their contributions were analyzed. The interaction force within the molecule of the Ni(II) complex was calculated, and finally the movable free region of the complex molecule in the unit cell was calculated and displayed. A hybrid ligand containing both Salamo and Salen structures was synthesized in a multi-step reaction. Based on the hybrid Salamo-Salen-Salamo-type ligand H 4 L, a mononuclear Ni(II) complex was synthesized and characterized by IR and UV-Vis spectroscopy, and the ratio of Ni(II) ion to H 4 L was demonstrated through UV-Vis titration spectroscopy. Theoretical UV-Vis spectra of H 4 L and its Ni(II) complex, HOMO-LUMO gaps and weak intramolecular interactions were studied through computational chemistry. [Display omitted] [ABSTRACT FROM AUTHOR]

• Two structurally different Co(II) Salamo-type complexes were synthesized and characterized structurally. • The varying degrees of distortion of the ligand have an undeniable impact on the formation of the two Co(II) complexes. • H 2 L and its Co(II) complexes were characterized by BVS, IRI and DFT calculation. A new non-symmetric salamo-type multidentate chelating ligand H 2 L (4-Formyl-6ʹ-methoxyl-2,2ʹ-[ ethylenedioxybis (nitrilomethylidyne)]diphenol) was designed and prepared. Two Co(II) complexes with different structures, [Co(L)(H 2 O)] (1) and [Co 2 (L) 2 ] 2 ·3CH 3 CN·2CH 3 OH (2) were prepared by the reactions of H 2 L with two different Co(II) salts (Co(OAc) 2 ·4H 2 O/CoCl 2 ·6H 2 O) in various organic solvents at an ambient temperature, respectively. Due to varying degrees of distortion of the ligand during the coordination reactions, the bonding modes of the ligand in complexes 1 and 2 are different. Complex 1 forms a penta-coordinated mononuclear, and complex 2 forms a penta-coordinated binuclear structure. By comparing UV–Vis and infrared spectroscopy of H 2 L with those of the corresponding complexes further characterize coordination between the ligand H 2 L and Co(II) ions. Theoretical calculations of DFT, BVS (Valence Bonding and Calculation), and IRI (Interaction Region Indicator) were used to show the different forces present in complexes 1 and 2 , and BVS calculations confirmed that Co is '+2′ valence in the complexes. Fluorescence property studies indicated that the possible mechanism for the decrease in fluorescence intensity upon binding of H 2 L to Co(II) ions is chelation fluorescence quenching. Based on a new non-symmetric Salamo-type ligand H 2 L, two penta-coordinated Co(II) complexes with different structures were synthesized and characterized structurally. Due to varying degrees of distortion of the ligand during the coordination reactions, the coordination modes of the ligand in the two complexes are different. Complex 2 contains two crystallographically independent but chemically identical molecules (molecules A and B). All the five Co(II) atoms possess distorted trigonal bipyramidal geometries. [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]

[Display omitted] Three new Co(II) complexes containing half-salamo type ligand HL viz. [Co(L)Cl] (1), [Co(L)(NO 3)] (2) and [Co(L)(NCS)] (3) were synthesized and characterized by single crystal X-ray diffraction. The results showed that the central Co(II) atoms in mononuclear complexes 1 – 3 are all located in the N 3 O cavity of the deprotonated ligand (L)− unit, while coordinated with different counteranions. The presence of counteranions in complexes 1 – 3 are Cl−, NO 3 − and NCS−, respectively. The spectral properties of these complexes were investigated in detail. In addition, the structural descriptions were corroborated with theoretical calculations. The Hirshfeld surface analysis combined with 2D fingerprint plots revealed the short-range intermolecular interactions of these complexes. [ABSTRACT FROM AUTHOR]

• A salamo-like coordination polymer Cd(II)-CP is successfully synthesized through insert auxiliary ligand. • The Cd(II)-CP is bifunctional sensor toward picric acid (PA) and S2−, which exhibit turn-off and turn-on fluorescence effects. • The sensor Cd(II)-CP can be used for the detection of PA and S2− in environmental water samples. A tailored Cd(II) coordination polymer [Cd(HL) 2 (1,4-pbyb)] n (Cd(II)-CP), has been synthesized successfully by using the host ligand H 2 L (4‑chloro-4ʹ‑bromo-6‑bromo-6ʹ‑tert‑butyl‑2,2ʹ-[ ethylenedioxybis (nitrilomethylidyne)]diphenol) and auxiliary ligand 1,4-di(pyridin-4-yl)benzene (1,4-pbyb) under the room temperature volatilization method. Single crystal X-ray diffraction experiment showed that Cd(II) atoms possess a slightly twisted hexa-coordinated octahedron configuration and Cd(II)-CP forms an infinite 1D zigzag-like chain configuration. The structural diversity of Cd(II)-CP is mainly attributed to the introduction of auxiliary ligand. The Cd(II)-CP is a highly selective and sensitive luminescent bifunctional chemosensor toward nitroaromatic compounds (NACs) and anions, which exhibits turn-off fluorescence effect on picric acid (PA) and turn-on fluorescence effect for sulfide ions (S2−). The sensing mechanisms were also carefully investigated. This study provides new conceptions for the design of CPs for detecting pollutants from surroundings, potentially mitigating health risks to humans and natural ecosystems. A customized Cd(II) coordination polymer [Cd(L) 2 (1,4-pbyb)] n (Cd(II)-CP), has been synthesized using the host ligand H 2 L with auxiliary ligand 1,4-pbyb. The Cd(II)-CP is highly selective and sensitive luminescent bifunctional chemosensor toward picric acid (PA) and S2−, which exhibits turn-off fluorescence effect on PA and turn-on fluorescence effect for S2−. [Display omitted] [ABSTRACT FROM AUTHOR]

A salamo-type coordination polymer [Cd(HL) 2 (4,4ʹ-bipy)] n (CP-Cd(II)) was synthesized by introducing the auxiliary ligand 4,4ʹ-bipy and used as a fluorescent chemical sensor to detect sulfur ions (S2−) and picric acid (PA). The sensor exhibits excellent selectivity and sensitivity for S2− and PA with fluorescence turn-on and off effects sequentially. [Display omitted] • The speedy and repeatable fluorescent sensor CP-Cd(II) was designed for sensing anions and nitro explosives. • The highest sensitivity and selectivity were observed for detection of sulfur ions (S2−) and picric acid (PA). • The sensor CP-Cd(II) can be used for the detection of S2− and PA in environmental water samples. A salamo-Cd(II) coordination polymer [Cd(HL) 2 (4,4ʹ-bipy)] n (CP-Cd(II)) was synthesized by introducing a auxiliary ligand 4,4ʹ-bipy to the host ligand H 2 L (4-chloro-4ʹ-bromo-6-bromo-6ʹ- tert -butyl-2,2ʹ-[ethylenedioxybis(nitrilomethylidyne)]di-phenol), and used as a fluorescent chemical sensor to detect sulfur ions (S2−) and picric acid (PA). Single crystal X-ray analysis demonstrated that the Cd(II) atom has a slightly distorted hexa -coordinate octahedron configuration and forms an infinite one-dimensional chain structure due to the intervention strategy of the auxiliary ligand. In fluorescence method, the sensor CP-Cd(II) exhibits good selectivity and sensitivity for S2− and PA with fluorescence turn-on and off effects sequentially. Additionally, the quenching efficiency of PA remains unchanged even after the sensor has been used for four cycles. At the same time, the sensor CP-Cd(II) can quickly detect S2− and PA within 10 s, which make them charming, recoverable and reliable luminescent coordination polymer sensor materials for detecting S2− and PA. The sensing mechanisms were attentively explored by mass spectrometry analysis, spectroscopic studies and density functional theory (DFT) calculations. Furthermore, the potential application of the sensor for further detection of S2− ions and PA in environmental systems was studied through actual water sample detection. [ABSTRACT FROM AUTHOR]

• A rigid bis(salamo)-like ligand H 4 L was designed and synthesized successfully. • A structurally novel tetranuclear Ni(II) complex was synthesized and characterized structurally, acetylacetone anions participate in the coordination as auxiliary bidentate ligands. • The Ni(II) complex was analyzed by MEPs and IRI, and the intermolecular interactions were clarified. Novel tetranuclear Ni(II) complex [Ni 4 (L)(acac) 4 (EtOH) 2 ]⋅4CH 2 Cl 2 was synthesized by a rigid bis(salamo)-like ligand H 4 L and Ni(acac) 2 in ethanol/dichloromethane mixed solvents, and characterized by different physicochemical methods. The X-ray diffraction result showed that all Ni(II) atoms are hexa-coordinated with slightly distorted octahedral geometries, and four Ni(II) atoms are correlated with each other through inversion. Acetylacetone anions acted as auxiliary ligands for bidentate chelation, and the monodentate ethanol molecules of solvent participated in the coordination. The properties of the ligand H 4 L and its Ni(II) complex were studied, including molecular electrostatic potential surface (MEPs), Hirshfeld surface and interaction region indicator (IRI) analysis. Through the above study, the reaction active sites were visualized, and the intermolecular interactions of the Ni(II) complex were clarified, which is consistent with the crystal structure of the Ni(II) complex. In addition, fluorescence spectra of the ligand H 4 L and its Ni(II) complex were investigated. Novel tetranuclear Ni(II) bis(salamo)-like complex [Ni 4 (L)(acac) 4 (EtOH) 2 ]⋅4CH 2 Cl 2 was synthesized and characterized structurally. All the Ni(II) atoms are hexa-coordinated with slightly distorted octahedral geometries, acetylacetone anions as auxiliary bidentate ligands participate in chelation. The reaction active sites were visualized, and the intermolecular interactions of the Ni(II) complex were clarified, which is consistent with the crystal structure of the Ni(II) complex. Fluorescence properties of H 4 L and its Ni(II) complex were investigated. [Display omitted] [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]

• A new kind of single‐armed salamo‐type ligand H 3 L and two corresponding Zn(II) complexes have been synthesized. • All of the Zn(Ⅱ) atoms in complexes 1 and 2 are penta-coordinated, highly distinct configurations are obtained because of the introduction of two kinds of counter-anions. • Fluorescence properties of H 3 L and complexes 1 and 2 were also investigated. Di- and tetra-nuclear Zn(II) complexes, [Zn 2 (L)(µ -OAc)(CH 3 OH)]·CH 3 OH (1) and [Zn 4 (L) 2 (OMe) 2 ]·2CH 3 COCH 3 ·CH 3 OH (2) have been successfully self-assembled by the reaction of a single‐armed salamo‐type ligand (H 3 L), Zn(OAc) 2 ·2H 2 O and Zn(NO 3) 2 ·6H 2 O, respectively. In the ligand H 3 L, tetradentate N 2 O 2 donor part of pocket I and NO 2 donor part of pocket II are designed to bond Zn(II) atoms, then unusually structural complexes were obtained by counteranion-driven self-assembled. Both complexes 1 and 2 are characterized by elemental analyses, IR spectra, UV-Vis spectra and single crystal X-ray diffraction. All of the Zn(II) atoms in complexes 1 and 2 are penta-coordinated, but highly distinct configurations are obtained because of the introduction of two kinds of counter-anions. In complex 1 , μ- OAc− counter-anion connects the two Zn(II) atoms in one ligand. In complex 2 , μ- OMe− counter-anions link the Zn(II) atoms within two ligand molecules and the structure of complex 2 is more complicated. What's more, in complex 1 , all Zn(II) atoms have the geometries of distorted trigonal bipyramid, while in complex 2 , all Zn(II) atoms have the geometries of distorted square pyramid. There are obvious π···π stacking interactions existing in complexes 1 and 2 , which are quantitatively valued by Hirshfeld surfaces analyses. Fluorescence properties are also investigated. Di- and tetra-nuclear Zn(II) complexes, [Zn 2 (L)(µ -OAc)(CH 3 OH)]·CH 3 OH (1) and [Zn 4 (L) 2 (OMe) 2 ]·2CH 3 COCH 3 ·CH 3 OH (2) have been successfully synthesized and structurally characterized. The fluorescence properties were also investigated. [Display omitted] [ABSTRACT FROM AUTHOR]

A new salamo-type probe H 2 L and its Co2+ complex [Co 3 (L) 2 (MeOH) 2 (μ -OAc) 2 ]·2MeOH were synthesized and characterized structurally. Fluorescence of Co2+ selectively response showed "off" when cations were sequentially detected. Meanwhile, the mechanism of recognition of Co2+ by H 2 L was got. DFT calculation and Hirshfeld surfaces analyses were investigated to further understand the experimental results observed. [Display omitted] • The probe H 2 L could efficiently detect Co2+ ion. • The probe H 2 L could detect Co2+. Meanwhile, H 2 L and Co2+ complex were characterized. • Hirshfeld surfaces analyses and DFT calculation were studied. A new salamo-type fluorescence probe H 2 L was synthesized by a series of reactions and corroborated by single-crystal X-ray crystallography and 1H NMR spectra. Fluorescence of Co2+ selectively response showed "off" when cations were sequentially detected. The LOD of H 2 L to Co2+ was calculated to be 3.73 × 10-7 M in DMF/water (9:1, v/v) solution system. Meanwhile, the single crystal of the Co2+ complex with H 2 L was obtained by solvent evaporation. The structure of the complex [Co 3 (L) 2 (MeOH) 2 (μ -OAc) 2 ]·2MeOH was validated by single-crystal X-ray diffraction, IR, and elemental analyses, and the mechanism of recognition of Co2+ by H 2 L was got. Density functional theory (DFT) and Hirshfeld surface analyses were investigated to further understand the experimental results observed. [ABSTRACT FROM AUTHOR]

A newly designed symmetrical multi-halogen-substituted bis(salamo)-based tetraoxime ligand H 3 L and its three penta-coordinated homo-binuclear Co(II) and Zn(II) complexes have been successfully synthesized and characterized structurally. Hirshfeld surfaces, DFT calculations and luminescences of the three complexes were investigated in detail. [Display omitted] A new symmetrical multi-halogen-substituted bis(salamo)-based tetraoxime ligand H 3 L and its corresponding penta-coordinated homo-binuclear Co(II) and Zn(II) complexes have been successfully synthesized. The three complexes, [{Co 2 (L)(OCH 3)} 2 ]·CHCl 3 (1), [{Zn 2 (L)(OCH 3)} 2 ]·CH 3 OH (2) and [{Co 2 (L)(OCH 2 CH 3)} 3 ]·2CH 3 CH 2 OH·CHCl 3 (3), have been characterized by elemental analyses, FT-IR and UV–Vis absorption spectroscopy as well as X-ray single-crystal structure analyses. In complexes 1 and 2 , two crystallographically independent but chemically identical binuclear complex molecules A and B were detected by X-ray analysis. However, in complex 3 , three crystallographically independent but chemically identical binuclear complex molecules A, B and C were detected. All the penta-coordinated Co(II) and Zn(II) atoms in complexes 1 and 2 are located in the N 2 O 2 cavities of the completely deprotonated (L)3- units and coordinated to one oxygen atom from one μ 2 -bridged methoxyl group. The coordination environment of the Co(II) atoms in complexes 1 and 3 are similar, except that the μ 2 -bridged methoxyl group is replaced with the μ 2 -bridged ethoxyl group. Additionally, both of complexes 1 and 3 form 3D supramolecular structures through abundant intermolecular interactions, while complex 2 forms 1D supramolecular structure through intermolecular hydrogen bonds. The C H···π interactions have been established in complexes 1 and 2 , where the π-system of H 3 L participates as π-donor. Through the means of Hirshfeld surfaces and 2D fingerprint plot analyses, existing different non-covalent supramolecular interactions in the Co(II) and Zn(II) complexes have been explained. Furthermore, to obtain a better understanding of the fluorescence properties of H 3 L and its complexes 1 – 3 , fluorescence titration experiments have been performed. [ABSTRACT FROM AUTHOR]