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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]

Two structurally different Cu(II) and Co(II) complexes, [Cu(L)] (1) and [Co2(L)2]⋅2CH3OH (2), constructed from a new polyhalogen-substituted unsymmetric salamo-based ligand (H2L, 4-chloro-4′-bromo-6-bromo-6′-tert-butyl-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol) were synthesized by wet-chemical methods. Complexes 1 and 2 were characterized through elemental analyses, IR and UV-vis spectroscopies and single crystal X-ray crystallography. In addition, the differences of the structures, electronic absorption characteristics and fluorescence property transitions from the ligand to complexes 1 and 2 were studied. The largest difference is that the ligand H2L can react with M(OAc)2 (M = Cu(II) and Co(II)) to give two complexes with distinct structures and behaviors. There are two chemically identical but crystallographically independent structural units (molecules A and B) in 1. Moreover, each Cu(II) ion (Cu1 or Cu2) is four-coordinate and possesses a square planar geometry, but both Co(II) ions of 2 are bridged by phenoxide ions and possess five-coordinate trigonal bipyramidal configurations. At the same time, Hirshfeld surface analyses showed there are short-range interaction features from the ligand to complexes 1 and 2, the O···H/H···O interactions of the ligand are significantly stronger than those of 1 and 2. [ABSTRACT FROM AUTHOR]

Three multinuclear Cu (II), Zn (II) and Cd (II) complexes, [Cu2(L)(μ‐OAc)]·CHCl2 (1), [Zn2(L)(μ‐OAc)(H2O)]·3CHCl3 (2) and [{Cd2(L)(OAc)(CH3CH2OH)}2]·2CH3CH2OH (3) with a single‐armed salamo‐like dioxime ligand H3L have been synthesized, and characterized by FT‐IR, UV–vis, X‐ray crystallography and Hirshfeld surfaces analyses. The ligand H3L has a linear structure and C‐H···π interactions between the two molecules. The complex 1 is a dinuclear Cu (II) complex, Cu1 and Cu2 are all five‐coordinate possessing distorted square pyramidal geometries. The complex 2 also forms a dinuclear Zn (II) structure, and Zn1 and Zn2 are all five‐coordinate bearing distorted trigonal bipyramidal geometries. The complex 3 is a symmetrical tetranuclear Cd (II) complex, and Cd1 is a hexa‐coordinate having octahedral configuration and Cd2 is hepta‐coordinate with a pentagonal bipyramidal geometry, and it has π···π interactions inside the molecule. In addition, fluorescence properties of the ligand and its complexes 1–3 have also been discussed. [ABSTRACT FROM AUTHOR]

Three newly designed containing‐PMBP N2O2‐donors complexes, [Co(L1)(CH3OH)2] (1), [{Zn(L2)(CH3OH)(H2O)}3] (2) and [Cu4(L2)4]⋅2CHCl3 (3), have been synthesized and structurally characterized using elemental analyses, infrared and UV–visible spectroscopies and single‐crystal X‐ray diffraction. X‐ray crystal structure determinations revealed that 1 consists of one Co(II) atom, one completely deprotonated (L1)2− unit and two coordinated methanol molecules. Complex 2 consists of three Zn(II) atoms, three completely deprotonated (L2)2− units, three coordinated methanol molecules and three coordinated water molecules. However, 3 includes four Cu(II) atoms, four completely deprotonated (L2)2− units and two crystallization chloroform molecules. The Co(II) and Zn(II) atoms in the structures of 1 and 2 adopt slightly distorted octahedral geometries. While, Cu(II) atoms in 3 can be best described as adopting slightly distorted square planar geometries. Complex 2 is a novel structure, and the ratio of H2L2 to Zn(II) atom is 3:3. In addition, two‐, three‐ and three‐dimensional supramolecular structures were constructed for 1, 2 and 3. Most importantly, Hirshfeld surface analysis of 1, 2 and 3 was conducted and fluorescence properties were investigated. [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]

One mononuclear Ni(II) complex [Ni(L1)(MeOH) 2 ]·MeOH(1) and two novel trinuclear Ni(II) complexes [Ni 3 (L2) 3 (EtOH) 6 ] (2) and [Ni 3 (L2) 3 (H 2 O) 6 ] (3) constructed from N 2 O 2 -donors chelating ligands (H 2 L1 and H 2 L2) were synthesized and characterized structurally. In addition, Hirshfeld surface analyses and the fluorescence titration experiments were investigated. One mononuclear Ni(II) complex [Ni(L1)(MeOH) 2 ]·MeOH (1) and two novel trinuclear Ni(II) complexes [Ni 3 (L2) 3 (EtOH) 6 ] (2) and [Ni 3 (L2) 3 (H 2 O) 6 ] (3) constructed from symmetric N 2 O 2 -donors chelating ligands (H 2 L1 and H 2 L2) were synthesized and characterized by elemental analyses, FT-IR, UV–Vis spectra and fluorescence spectra. The structures of all three complexes were confirmed by single crystal X-ray diffraction analyses. Complex 1 includes one Ni(II) atom, one completely deprotonated (L1)2− unit and two coordinated methanol molecules, and forms an infinite 2D supramolecular network via the intermolecular hydrogen bonds. While complex 2 or 3 is trinuclear with three Ni(II) atoms, three completely deprotonated (L2)2− units and six coordinated ethanol or H 2 O molecules. These self-assembling complexes form different dimensional supramolecular structures through inter- and intramolecular hydrogen bonds. Hirshfeld surface analyses for complexes 1 , 2 and 3 were mapped with various functions and further quantification of intermolecular interactions was made through the generation of 2D fingerprint plots. In addition, the fluorescence titration experiments were used to characterize fluorescence properties of complexes 1 and 2. [ABSTRACT FROM AUTHOR]

Graphical abstract The self-assembling of di-, tri- and tetra-nuclear metal(II) complexes shows propeller, butterfly and windmill type motifs, respectively. In complexes 1 and 2 , the ideal size, shape as well as strong coordination ability of OAc− as an anion significantly stabilize the aesthetic structure, while in complex 3 , the hydroxyl radical of an unexpected ligand H 2 L′, which derived from the cleavage of HL are coordinated with three Co(II) atoms at the same time. Meanwhile, complexes 1 , 2 and 3 possess a self-assembling 2D, 3D and 0D supramolecular structures by abundant noncovalent interactions. Besides, magnetic properties and Hirshfeld surface analyses were discussed. Abstract Two newly di- and tri-nuclear Cu(II) and Ni(II) complexes constructed from a half-salamo chelating ligand (HL: 2-[ O -(1-ethyloxyamide)]oxime-6-methoxyphenol), [Cu 2 (L) 2 (μ-OAc) 2 ] (1) and [{Ni 3 (μ-OAc) 2 (L) 2 (OAc) 2 ]·CHCl 3 (2), and one tetranuclear Co(II) complex [Co 4 (L′) 4 (MeOH) 4 ] (3) based on an unexpected ligand H 2 L′ derived from the cleavage of HL have been synthesized and characterized by elemental analyses, IR, UV–vis spectra, and single crystal X-ray diffraction analyses. The single crystals of complexes 1 , 2 and 3 in the process of synthesis are obtained through different routes. The complex 1 includes two Cu(II) atoms, two completely deprotonated (L)− units and two μ-acetate ions, which displays a propeller-type motif. The complex 2 contains three Ni(II) atoms, two completely deprotonated (L)− units, two μ-acetate ions, two chelating acetate ions and one crystallizing chloroform molecule, the crystal structure of complex 2 reveals a butterfly-type motif. The complex 3 is made up of four Co(II) atoms, four completely deprotonated (L′)2− units (HL′: 2-[ O -(1-hydroxyethyl)]oxime-6-methoxyphenol) and four coordinated methanol molecules, which shows a windmill-type motif. Besides, magnetic properties and Hirshfeld surface analyses were discussed. [ABSTRACT FROM AUTHOR]

Two unusual heterobimetallic [CuII 4 LnIII 2 ] complexes were constructed from a N 2 O 2 - and O 6 -donor bis(salamo)-based ligand (H 4 L), and characterized structurally. The intermolecular interactions were quantitatively analyzed by Hirshfeld surfaces, as well as, fluorescence properties have also been studied. [Display omitted] • Two structurally novel heterobimetallic hexanuclear [CuII 4 LnIII 2 ] complexes were prepared using a designed N 2 O 2 - and O 6 -donor bis(salamo)-based ligand. • The different natures of three-compartmental H 4 L lead to the site‐selective introduction of two various metalII/III atoms. • Quantitative analyses of intermolecular interactions were evaluated by Hirshfeld surfaces analyses. • The fluorescence properties were further discussed. Two unusual heterobimetallic [CuII 4 LnIII 2 ] complexes, [{Cu 4 (L) 2 La 2 (ƞ 2-NO 3) 6 (EtOH)}]·2Me 2 CO (1) and [{Cu 4 (L) 2 Ce 2 (ƞ 2-NO 3) 6 (EtOH)} 2 ]·4Me 2 CO·MeOH (2) were constructed from a N 2 O 2 - and O 6 -donor bis(salamo)-based ligand (H 4 L). The structures were characterized by physical chemistry and spectroscopy methods. The two complexes 1 and 2 have similar structures, two heterotrinuclear parts with the same structure are linked by the coordination between one CuII atom and oxime-type oxygen atoms to obtain the heterohexanuclear complexes 1 and 2. Four penta-coordinate CuII atoms are located at the N 2 O 2 cavities of the ligand (L)4- units, two LaIII/CeIII atoms are surrounded by the open-chain 18-crown-6 (O 6) coordination environment. At the same time, eight bridged phenol oxygen atoms connect the six CuII/LnIII atoms. Infinite three-dimensional supra-molecular structures are formed in complexes 1 and 2 through H-bonds. The intermolecular interactions were quantitatively analyzed by Hirshfeld surfaces, as well as, fluorescence properties have also been studied. [ABSTRACT FROM AUTHOR]

• The pyridine-including half-salamo-like ligands HL1 and HL2 have been developed successfully. • Two first Co(III) complexes, [Co(L1)(N 3) 2 ] (1), and [Co(L2)(N 3) 2 ] (2) were synthesized and ascertained structurally. • The complexes 1 and 2 are unusual salamo-like Co(III) complexes with variable valence. This situation has never reported in the previous salamo-based complexes. Two structurally novel Co(III) complexes have been successfully constructed from the pyridine-including half-salamo-like ligands (HL1 and HL2), namely as [Co(L1)(N 3) 2 ] (1) and [Co(L2)(N 3) 2 ] (2). The structural features of complexes 1 and 2 have been confirmed by means of single crystal X-ray diffraction experiment. The structural studies revealed that complexes 1 and 2 have similar structures. The characterization of the two ligands and their Co(III) complexes was ascertained by means of infrared spectra, ultraviolet spectra and Hirshfeld surfaces analyses. In addition, compared with the ligands HL1 and HL2, the fluorescence intensities of the corresponding complexes 1 and 2 decreased significantly. When Co(II) salt was gradually added to the ligand solution, the intensity of the fluorescence emission peak decreased with the continuous addition of Co(II) salt until this trend stopped, which indicates that the introduction of Co(II) ion leads to the charge transfer from the ligand to Co(III) ion. Two structurally novel Co(III) complexes have been successfully constructed from the pyridine-including half-salamo-like ligands (HL1 and HL2), namely as [Co(L1)(N 3) 2 ] (1) and [Co(L2)(N 3) 2 ] (2). The characterization of the two ligands and their Co(III) complexes was ascertained by means of infrared spectra, ultraviolet spectra, X-ray crystallography, fluorescence spectra and Hirshfeld surfaces analyses. [Display omitted] [ABSTRACT FROM AUTHOR]

Three novel N 4 -cavity Cu(II), Ni(II) and Zn(II) complexes were successfully synthesized via the reactions of a novel pyridine-containing N 4 -cavity bisoxime ligand L. All three complexes are monoclinic systems. Complexes 2 and 3 form centrosymmetric helical molecules. Complexes 1 – 3 have been characterized by elemental analysis, IR, UV–Vis spectroscopy and single crystal X-ray crystallography. In addition, supramolecular interactions, Hirshfeld surface analysis to analyze the crystal properties have been studied. [Display omitted] • A novel ligand L with N4 cavity was synthesized and characterized. • Three excess metal single crystals were synthesized via the ligand L. • Hirshfeld surface analysis was performed on single crystals. Three novel N 4 -cavity Cu(II), Ni(II) and Zn(II) mononuclear complexes, [Cu(L)(NO 3) 2 ][Cu(L)(NO 3)]NO 3 (1) [Ni(L)(NO 3) 2 ] (2) and [Zn(L)(NO 3) 2 ] (3) were successfully synthesized via the reactions of a pyridine-containing N 4 -cavity bisoxime ligand L (L = 2,2′-[Ethylenedioxobis(azetidinyl)]pyridine) with Cu(II), Ni(II) and Zn(II) nitrates, respectively. Complexes 1 – 3 were characterized via elemental analysis, IR, UV–Vis spectra and X-ray crystallography. All three complexes are monoclinic systems, containing one M(II) atom and one (L) ligand moiety. Complexes 2 and 3 form centrosymmetric molecules. In addition, supramolecular interactions, Hirshfeld surface analysis were used to analyze the crystal properties that have been studied. [ABSTRACT FROM AUTHOR]

Two newly designed tetranuclear metal(II) complexes, [{Co(L)(μ -OAc)Co(CH 3 OH) 2 } 2 and [{Ni(L)(DMF)(μ -OAc)Ni} 2 derived from an unsymmetrical salamo-like ligand (H 3 L: 6-hydroxy-6′-methoxy-2, 2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol) were synthesized and characterized by elemental analyses, infrared spectroscopy, ultraviolet–visible absorption spectroscopy, fluorescence spectroscopy, X-ray single crystal diffraction and Hirshfeld surfaces analyses. • Tetranuclear Co(II) and Ni(II) complexes were synthesized and characterized structurally. • The crystal structures of Co(II) and Ni(II) complexes are very interesting. • Hirshfeld surfaces and fluorescent properties of the Co(II) and Ni(II) complexes were investigated. Two newly designed tetranuclear transition metal(II) complexes, [{Co(L)(μ -OAc)Co(CH 3 OH) 2 } 2 and [{Ni(L)(DMF)(μ -OAc)Ni} 2 derived from an unsymmetrical salamo-like donor-N 2 O 4 ligand (H 3 L: 6-hydroxy-6′-methoxy-2, 2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol) were synthesized and characterized by elemental analysis, FT-IR, UV-vis, fluorescence spectroscopy, X-ray crystallography and Hirshfeld surface analysis. The Co(II) complex includes two fully deprotonated (L)3− moieties, two μ-acetato ligands and four coordinated methanol molecules, bearing a highly symmetrical tetranuclear structure. The terminal Co(II) ions are penta-coordinated and have slightly twisted triangular bipyramidal geometries, and the central Co(II) ions are hexa-coordinated and possess slightly twisted octahedral geometries. The Co(II) complex was self-assembled by adequate intermolecular hydrogen bonding interactions giving rise to an infinite two-dimensional supramolecular structure. The Ni(II) complex adopts a symmetric tetranuclear structure including two fully deprotonated (L)3− units, two coordinated DMF molecules, and two μ-acetato ligands. All the Ni(II) ions are hexa-coordinated and have slightly twisted octahedral geometries. At the same time, the fluorescent properties and Hirshfeld surfaces analyses of the Co(II) and Ni(II) complexes were also investigated in detail. [ABSTRACT FROM AUTHOR]