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A structurally novel bi-nuclear Co(III) complex ([Co2(L)2(H2O)2]) was prepared by the reaction of a single-armed salamo-like ligand H3L and Co(II) acetate tetrahydrates in methanol solution and characterized structurally. The crystallography data revealed that the Co(III) complex is bi-nuclear, and composed of two Co(III) atoms, two fully deprotonated ligand (L)3− units and two coordinated H2O molecules. This structurally novel Co(III) complex is different from the previously reported complexes derived from other similar single-armed salamo-like ligands. Each Co(III) atom partially occupies the N2O2 cavity of the ligand (L)3− unit and the NO3 cavity of another deprotonated ligand (L)3− unit. Significantly, divalent Co(II) ions are oxidized to trivalent Co(III) ions upon coordination with the ligand (L)3− units. Emission spectrum studies showed that the Co(III) complex is fluorescence quenched. Hirshfeld surfaces analyses revealed that H⋅⋅⋅H interaction contributes the most to the 2D fingerprinting map. The bi-nuclear Co(III) single-armed salamo-like complex [Co2(L)2(H2O)2] has been successfully synthesized and structurally characterized. The fluorescence properties and Hirshfeld surfaces analyses of H3L and its Co(III) complex were investigated. [ABSTRACT FROM AUTHOR]

A quinoline-containing semi-salamo-type ligand, HL, was synthesized and a dinuclear Ni(II) complex, [Ni2(L)2(NCS)2], was produced. The complex was experimentally analyzed by elemental analysis, fluorescence, and UV–Vis spectroscopy. X-ray single crystal diffraction experiments showed that the complex is a six-coordinate, structurally symmetric, phenoxy-bridged dinuclear Ni(II) dimer with the participation of SCN− in the coordination to satisfy charge neutrality. The self-assembly forms a 2-D supramolecular network structure through hydrogen bonding and π⋯π interactions. DFT calculations were performed on the complex to analyze its energy gaps, and UV–Vis experiment was verified by TD-DFT calculation. In addition, close intermolecular contacts were investigated by Hirshfeld surface analysis to quantify the crystal structure interaction. [ABSTRACT FROM AUTHOR]

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 solvent-induced bis(phenoxo)-acetate-bridged binuclear Ni(II) complexes, [Ni2(L)(µ-OAc)(CH3OH)] (1) and [Ni2(L)(µ-OAc)(H2O)] (2), were synthesized with a bis(salamo)-like ligand H3L and Ni(OAc)2·4H2O in two different alcohol solvents (methanol and ethanol). Complexes 1 and 2 were described by elemental analyses, single crystal X-ray diffraction, IR spectra, UV–vis spectra and fluorescence spectra. Complexes 1 and 2 have analogous crystal structures, but the non-covalent interactions are distinct. The one-dimensional chain of 1 is formed by π–π interactions, and the three-dimensional supramolecular network structure of 2 is formed by intermolecular hydrogen bonding interactions. In addition, fluorescence experiments indicated that the fluorescence of 1 and 2 undergoe a significant quenching compared to H3L. Intermolecular forces were investigated using Hirshfeld surface analysis. DFT calculations showed that 1 and 2 have high chemical reactivity and low kinetic stability. [ABSTRACT FROM AUTHOR]

A penta-coordinated dinuclear Zn(II) complex, [Zn2(L)(μ-PhCOO)(EtOH)] (1), and a hexa-coordinate tetranuclear Cd(II) complex, [{Cd2(L)(EtOH)(η-OAc)}2]·2CH2Cl2 (2), have been synthesized by reactions of a single-armed salamo-based ligand, H3L, and two kinds of transition metal salts, (Zn(NO3)2·6H2O and Cd(OAc)2·2H2O), respectively. Complexes 1 and 2 have been characterized by elemental analyses, single crystal X-ray diffraction, IR spectra and UV-Vis spectra. Complex 1 is composed of a totally deprotonated ligand (L)3- moiety, two Zn(II) ions, one μ-PhCOO- counter-anion and one coordinated ethanol molecule. The (L)3- unit packages two Zn(II) ions, the μ-PhCOO- counter-anion bridges two adjacent Zn(II) ions and one ethanol molecule coordinates with the Zn2 ion, so that both Zn(II) ions are penta-coordinated with slightly distorted trigonal bipyramidal configurations, and the τ5 values of Zn1 and Zn2 are 0.86 and 0.65, respectively. Complex 2 consists of two discrete and similar electroneutral tetra-nuclear units, 2 A and 2B, and two crystallized dichloromethane molecules. Each unit has a symmetric structure that is made up of two completely deprotonated ligand (L)3- moieties, four Cd(II) ions, two η-OAc- counter-anions and two coordinated ethanol molecules. Fluorescence properties and Hirshfeld surfaces analyses have been studied as well. [ABSTRACT FROM AUTHOR]

A relatively rigid acyclic salamo-type ligand H2L and its square planar Cu(II) complex, [Cu(L)]·CH3OH, were synthesized and characterized by X-ray crystallography, as well as Fourier-transform infrared spectra, UV–Vis spectra, Hirshfeld surface analyses and DFT calculations. The ligand crystallizes in monoclinic space group P 21/c and has pairs of intramolecular hydrogen bonds between the oxime nitrogen atoms and the hydroxyl groups. The Cu(II) complex crystallizes in the monoclinic space group P 21/c. The Cu(II) ion is located in the N2O2 cavity of the fully deprotonated salamo-type ligand (L)2− unit, thus forming a four-coordinate distorted square planar geometry. At the same time, a belt-like, 2-D supramolecular structure is formed by the interaction of intermolecular hydrogen bonds, and the intermolecular interaction force is quantitatively analyzed by Hirshfeld surfaces. Significantly, fluorescence properties of the ligand and its Cu(II) complex were also studied. The coordination ratio of the Cu(II) complex was proved by UV–Vis and fluorescence titration experiments. [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]

A family of rare structurally different homometal multinuclear CuII bis(salamo)‐based complexes, [Cu4(L)2(MeOH)2](ClO4)2·2MeOH (1), [Cu4(L)2(EtOH)2](NO3)2·2EtOH (2) and [Cu2(HL)(EtOH)Br2]·CHCl3 (3), has been successfully synthesized by the reactions of cupric salts with a bis(salamo)‐based multidentate chelate ligand (H3L). The salamo‐based ligand [R‐CH=N—O—(CH2)n—O—N=CH—R] is a new type of salen‐based analog. Complexes (1) and (2) are isostructural structures, and crystallize in monoclinic space group P21/n with centrosymmetric spiral structures, where the main structures contain two fully deprotonated ligand (L)3− units, a charged tetranuclear CuII folding center and two coordinated solvent molecules. Complex (3) crystallizes in monoclinic space group Cc and consists of two CuII cations, one incompletely deprotonated ligand (HL)2− unit and one coordinated ethanol molecule, and forms a novel homo‐binuclear CuII complex structure due to Br− counter anions. Complexes (1)–(3) have zero‐dimensional cluster‐based structures and are further assembled into three‐dimensional frameworks via intermolecular interactions. Because of the different solvents and counter anions which have a significant influence on the structures of complexes (1)–(3), the interactions were quantitatively evaluated by Hirshfeld surfaces analyses. Complexes (1)–(3) have been characterized by elemental analyses, IR spectra, UV–vis spectra and X‐ray crystallography analyses. In addition, fluorescence properties are evaluated and DFT calculations are performed. [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]

Two newly designed heteromultinuclear [CuII4SmIII2] and [CuII2TbIII] bis (salamo)‐based complexes, [{Cu2(L)Sm (NO3)2(μ2‐NO3)(CH3OH)}2]·2CH3OH and [Cu2(L)Tb (NO3)2(μ2‐NO3)][Cu2(L)Tb (NO3)2(μ2‐NO3)(H2O)]·CH3OH, were synthesized and characterized by elemental analyses, Fourier transform infrared (FT‐IR) spectra, ultraviolet–visible (UV–vis) absorption spectra, and X‐ray crystallography. The ultraviolet titration experiments exhibited that the coordination ratio of the ligand, rare earth metal, and transition metal is 1:1:2. In the [CuII4SmIII2] complex, Cu1 atom has a distorted quadrilateral pyramid geometry, whereas Cu2 atom forms a slightly distorted octahedral geometry. The [CuII2TbIII] complex unit cell contains two crystallographically independent and chemically different heterotrinuclear complexes (Molecules A and B). In Molecule A, the Cu1 atom bears a four‐coordinated plane quadrilateral geometry, whereas the five‐coordinated Cu2 atom forms a slightly distorted tetragonal cone geometry. In Molecule B, the five‐coordinated Cu3 and Cu4 atoms possess slightly distorted tetragonal cone geometries. Noncovalent interactions like hydrogen bonding and π···π stacking interactions are operative in construction of supramolecular architectures. The [CuII2TbIII] complex behaves as a catalyst towards oxidative coupling of 2‐AP in MeCN medium. In addition, fluorescence properties of the ligand H4L and its [CuII4SmIII2] and [CuII2TbIII] complexes have also been discussed. [ABSTRACT FROM AUTHOR]

• A double-armed salamo-like ligand was developed. • The crystal structure of the first double-armed salamo-like M(II) complex was reported. • The presence of two bridged acetate groups plays a crucial role in the stability of the complex. • Fluorescence properties and theoretical calculations were investigated. The first double-armed salamo-based tri-nuclear Ni(II) complex, named as [Ni 3 (L)(μ 2 -OAc) 2 ]·3CHCl 3 was successfully self-assembled, and elucidated via elemental analyses, spectroscopic technology and theoretical analyses. The results indicated that one ligand H 4 L has coordinated with three Ni(II) atoms in a 1:3 ratio unreported previously. One of the three Ni(II) atoms is located at the cavity of the N 2 O 2 donor, while other two Ni(II) atoms are sited at the NO 2 cavities formed by double-armed salicylaldehyde moieties, respectively, and further coordinated via two bridging μ 2 -acetate groups, which is a quite novel structure. The fluorescent properties and a range of theory calculations in the ligand and its Ni(II) complex were researched in detail. A novel double-armed salamo-like tri-nuclear Ni(II) complex, [Ni 3 (L)(μ-OAc) 2 ]·3CHCl 3 was successfully self-assembled for the first time. X-ray single-crystal diffraction results showed that the Ni(II) complex is formed by a 1:3 coordination ratio between H 4 L and three Ni(II) atoms and presents a novel structure. Besides, infrared spectroscopy, UV-vis spectroscopy, a series of theoretical calculations and fluorescence properties of H 4 L and its Ni(II) complex were studied. [Display omitted] [ABSTRACT FROM AUTHOR]

• The quinoline-decorated N 3 O-donor half-salamo type ligand HL was designed and synthesized. • Two novel Co(Ⅱ) complexes [Co(L)Cl] (1) and [Co(L)(NCS)] (2) were obtained by the reaction of HL with different Co(Ⅱ) salts. • Quantitative analyses of intermolecular interactions in the crystalline structures were performed by Hirshfeld surfaces analysis. Self-assembly through a quinoline-decorated N 3 O donor half-salamo-type tetradentate ligand HL and coordinative preference of Co(II) ion, two novel Co(II) complexes [Co(L)Cl] (1) and [Co(L)(NCS)] (2) were synthesized and characterized. X-ray crystallography revealed that both complexes 1 and 2 have similar mononuclear structure, in which the five-coordinated Co(II) atoms are not only surrounded by the N 3 O cavity of the deprotonated ligand (L)− unit, but also coordinated with different Cl− and NCS− anions. For the involvement of different anions, the crystal structures of the two complexes exhibit intermolecular C H···Cl and C H···S hydrogen interactions in building supramolecular assemblies, respectively. The two complexes are stabilized by C H···O, C H···N, C H···C, C H···S bonds and C H···π, π···π interactions. The spectral properties of the complexes were investigated through UV–Vis and fluorescence spectroscopy. In addition, the detailed analyses of Hirshfeld surfaces and fingerprint plots provide the basis of the intermolecular interactions in building crystal blocks. Two novel Co(II) complexes, [Co(L)Cl] (1) and [Co(L)(NCS)] (2) with a quinoline-decorated half-salamo type ligand HL were synthesized and characterized structurally. In addition, spectroscopic properties, DFT calculations and Hirshfeld surfaces analyses of HL and its two Co(II) complexes were investigated in detail. [Display omitted] [ABSTRACT FROM AUTHOR]

• Complexes 1 and 2 were successfully prepared and characterized structurally. • Complex 2 is not obtained from H 3 L but from a new ligand H 2 L1. • Theoretical calculations and fluorescence properties were investigated in detail. Two unusual bis(salamo)-based Co(II) complexes, [Co 2 (L)(OMe)]·2MeOH (1) and [Co 4 (L1) 4 (MeOH) 4 ] (2) were designed and successfully prepared, and characterized structurally. The crystal structure analysis showed that complex 1 is composed of one fully deprotonated ligand (L)3− moity, two divalent Co(II) atoms and one bridge-coordinated methanol molecule, while complex 2 is an asymmetric homotetranuclear structure made up of four Co(II) atoms, four fully deprotonated (L1)2− units and four coordinated methanol molecules. It is noteworthy that the reaction of cobalt(II) nitrate with H 3 L produces complex 2. This complex is not obtained from the original ligand H 3 L but from a new ligand H 2 L1. Therefore, the phenomenon can be used to prepare metal(II/III) complexes with excellent structure. The molecular frontier orbitals HOMO and LUMO of H 3 L and complexes 1 and 2 were analyzed by DFT calculations, and the results showed that the energy gaps of the complexes were reduced due to the combination of the orbitals compared to the ligand. The reaction sites of H 3 L with Co(II) atoms were analyzed by ESP studies, and the results showed that the crystal structures of the complexes are consistent with the theoretical predictions. Hirshfeld surface analyses indicated the different interactions in the complexes, and revealed that the main contributions to the crystal stacking were from H H, C H and H O interactions. The interactions in the complexes were further explored by IRI research, the results exhibited that there are abundant interactions in complexes 1 and 2 , which are important for their construction of supramolecules. The fluorescence strengths of complexes 1 and 2 are significantly lower compared to H 3 L, which can be attributed to the ligand to metal charge transition (LMCT). [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 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]

• Poly-nuclear Zn(II) and Ni(II) salamo-type complexes were synthesized and characterized structurally. • The decoordination sites of the aldol condensation reaction leads to the occurrence of self-assembly. • Fluorescence properties and theoretical calculations of complexes 1 and 2 were explored. Based on a salamo-type ligand H 2 L containing a bare formyl group, a di-nuclear salamo-Zn(II) complex [Zn 2 (L)Cl 2 ] (1) was synthesized. With the occurrence of Claisen-Schmidt reaction catalyzed by triethylamine, the O 4 coordination environment of the H 2 L ligand is destroyed, producing a new ligand H 2 L′. Which conflicts with the characteristics of Ni(II) atoms that are generally multi-coordinate, driving the occurrence of self-assembly reaction, and obtaining a tetra-nuclear salamo-Ni(II) complex [Ni 4 (L′) 2 (µ 2 -Cl) 2 (µ 3 -OMe) 2 (EtOH) 2 ] (2). X-single crystal diffraction analyses showed that two Zn(II) atoms in the salamo-Zn(II) complex occupy the cavities of N 2 O 2 and O 4 , respectively, while Ni1 and Ni1# atoms in the salamo-Ni(II) complex occupy the N 2 O 2 cavities from two H 2 L′ ligands, there are many bridges (µ 2 -Cl− & µ 3 -OMe− aions) between Ni2 and Ni2# atoms. The UV–Vis titration experiments demonstrated the binding ratio of H 2 L to Zn(II) atoms is 1:2, while the binding ratio of the ligand H 2 L′ to Ni(II) atoms is also 1:2, the results are consistent with the X-ray single crystal structures. Through DFT calculation, the single-point energy of complexes 1 and 2 and the optimized structure of the ligand H 2 L were found that the softness of HOMO-LUMO gap of salamo-Zn(II) complex is small and not easy to deform, and the softness of salamo-Ni(II) complex is large and easy to deform, which is in agreement with the calculated results of intra-molecular interactions in IRI. The interaction of a large number of hydrogen bonds, C-H...π, π...π, van der Waals forces and so on in salamo-Ni(II) complex makes it easy to deform. The fluorescence properties of H 2 L and the salamo-Zn(II) complex have also been studied. Based on a salamo-type ligand H 2 L containing a bare formyl group, a di-nuclear salamo-Zn(II) complex [Zn 2 (L)Cl 2 ] (1) was synthesized. With the occurrence of the Claisen-Schmidt reaction catalyzed by triethylamine, the O 4 environment of the H 2 L ligand is destroyed, producing a new ligand H 2 L'. Which conflicts with the characteristics of Ni(II) atoms that are generally multi-coordinate, driving the occurrence of self-assembly reaction, and obtaining a tetra-nuclear salamo-Ni (II) complex [Ni 4 (L') 2 (µ 2 -Cl) 2 (µ 3 -OMe) 2 (EtOH) 2 ] (2). Fluorescence properties and a range of theoretical calculations complexes 1 and 2 were investigated in detail. [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]

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]

• 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]

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]

• A new heterobimetallic [Cu(II) 2 Pr(III)] complex with a symmetric flexible bis(salamo)-type ligand was synthesized and characterized structurally. • There are two different metal-binding sites of N 2 O 2 and O 6 (two being specific for the 3d metal ions and the other for the 4f metal ion) for the synthesis of heteropolynuclear 3d-4f complex with a flexible bis(salamo)‐type ligand. • Hirshfeld surface analysis and luminescence of the [Cu(II) 2 Pr(III)] complex was investigated. A new heterobimetallic 3d-4f [Cu(II) 2 Pr(III)] complex [Cu 2 Pr(L)(ƞ 2-NO 3) 3 (EtOH) 2 ]·2EtOH with a symmetric flexible bis(salamo)-type ligand, (1E,1′E)-2,3-dihydroxynaphthalene-1,4-dicarbaldehyde O,O -di(3-((((E)-3-ethoxy-2-hydroxybenzylidene)amino)oxy)propyl)dioxime (H 4 L), has been synthesized and characterized structurally. Single crystal X-ray diffraction analysis showed that the ligand was fasten by different metal ions to form a hetero-trinuclear complex with C-shaped structure, where two N 2 O 2 -donors of the completely deprotonated ligand (L)4− unit and two oxygen atoms from two ethanol molecules coordinate with Cu(II) atoms (Cu1, Cu2), respectively, to form two five-coordinated square pyramid geometries. Meanwhile, where the O 6 cavity coordination sphere of the ligand (L)4− unit and six oxygen atoms from three nitrate groups coordinate with the Pr(III) atom together to form a twelve-coordinated icosahedron. Due to the Cu(II) atom in the O 6 cavity was replaced by the Pr(III) atom, it shows that the hetero-trinuclear complex after self-assembly is more stable than the homo-trinuclear complex. At the same time, through UV–Vis titration spectrometric analysis, we can observed that the hetero-trinuclear [Cu(II) 2 Pr(III)] complex is obtained by 1 equiv. Pr(NO 3) 3 ·5H 2 O and 2 equiv. Cu(NO 3) 2 ·3H 2 O and 1 equiv. H 4 L. Significantly, fluorescence properties and Hirshfeld surfaces analyses of the [Cu(II) 2 Pr(III)] complex was also studied. A new heterobimetallic [Cu(II) 2 Pr(III)] complex with a symmetric flexible bis(salamo)-type ligand, (1E,1′E)-2,3-dihydroxynaphthalene-1,4-dicarbaldehyde O,O-di(3-((((E)-3-ethoxy-2-hydroxybenzylidene)amino)oxy)propyl)dioxime (H 4 L), has been synthesized and characterized structurally. Two five-coordinated Cu(II) atoms and one twelve-coordinated icosahedron Pr(III) atom are located in different coordination environments, respectively, fluorescence properties, Hirshfeld surfaces analyses and DFT calculations of the [Cu(II) 2 Pr(III)] complex was also studied. [Display omitted]. [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]

Two octahedral homopolynuclear Ni(II) complexes, [Ni 2 (L)(OAc)(MeOH)]·CH 3 CN·MeOH (1) and [Ni 4 (L) 2 (acac) 2 (EtOH) 2 ]·2CH 3 CN (2) have been synthesized and characterized structurally. Hirshfeld surfaces, DFT calculation and fluorescence properties of complexes 1 and 2 were investigated. [Display omitted] • Anion-solvent-dependent construction of two homopolynuclear Ni(II) complexes 1 and 2 were synthesized and characterized structurally. • Complex 2 possesses a novel centrosymmetric tetra-nuclear structure with two dinuclear [Ni 2 (L)(acac)(EtOH)] units. • Hirshfeld surfaces, DFT calculation and fluorescence properties of complexes 1 and 2 were investigated. Two counteranion-solvent-dependent homopolynuclear Ni(II) complexes, [Ni 2 (L)(OAc)(MeOH)]·CH 3 CN·MeOH (1) and [Ni 4 (L) 2 (acac) 2 (EtOH) 2 ]·2CH 3 CN (2) have been constructed by exploiting the flexibility of a symmetrical multi-halogen-substituted bis(salamo)-based ligand H 3 L. The structures of complexes 1 and 2 were confirmed by single crystal X-ray diffraction studies. Complex 1 is a di-nuclear Ni(II) complex, where two octahedral Ni(II) atoms are located in the N 2 O 2 cavities of the salamo units, and bridged via a acetate ion. Complex 2 possesses a centrosymmetric tetra-nuclear structure with two di-nuclear [Ni 2 (L)(acac)(EtOH)] units. It is worth noting that one acetylacetonate anion is coordinated to Ni2 atom in bidentate fashion along with one methanol molecule that completes its hexa-coordinated geometry. It is possible that the existence of the acetylacetone anion makes the ligand (L)3- unit exhibit its flexibility, which promotes the formation of tetra-nuclear complex 2. The close surveillance of the crystal structure of complexes 1 and 2 discloses some notable non-covalent interactions like H-bonding, C H⋯π and π⋯π. Moreover, both complexes 1 and 2 form three-dimensional supramolecular structures with the help of intermolecular hydrogen bonds. It was found that the synthesis of complexes 1 and 2 weakened the fluorescence intensity of H 3 L until quenching. Hirshfeld surfaces analyses confirmed that hydrogen bond interactions play the most important role in the stability of crystal structures. The high kinetic stability and low chemical reactivity of complexes 1 and 2 were investigated based on the band gap energy. [ABSTRACT FROM AUTHOR]

The multinuclear Co(II) and Zn(II) salamo-based complexes [{Co 2 (L)(μ -OMe)} 8 ]·11CH 3 OH·2H 2 O (1) and [Zn 2 (L)(μ -OEt)]·CHCl 3 (2) have been successfully synthesized by the solvent evaporation method and characterized structurally. Complexes 1 and 2 are examples of crystallographically independent but chemically identical molecules with rare τ 5 parameters. [Display omitted] The multinuclear Co(II) and Zn(II) salamo-based complexes [{Co 2 (L)(μ -OMe)} 8 ]·11CH 3 OH·2H 2 O (1) and [Zn 2 (L)(μ -OEt)]·CHCl 3 (2) have been successfully isolated by the solvent evaporation method and characterized structurally by elemental analyses, IR spectra and UV–Vis spectra. Complex 1 consists of four closely related neutral dinuclear units, 1A , 1B , 1C and 1D , while complex 2 consists of three closely related neutral dinuclear units 2A , 2B and 2C. Complexes 1 and 2 are unique examples of crystallographically independent but chemically identical molecules with unique τ 5 parameters. For complex 1 , all the Co(II) atoms possess extremely distorted trigonal bipyramidal geometries, except the for Co4 atom, with the Co(II) atoms lying out of the plane of the equatorial donor atoms. For complex 2 , except for the Zn5 atom, the Zn(II) atoms possess extremely distorted trigonal bipyramidal geometries and square-based pyramidal geometries. Significantly, the geometries about the Co4 and Zn5 atoms show τ 5 values very close to 0.500 and there are few such examples like those. Complex 2 has an obvious fluorescence enhancement, which may be caused by intramolecular charge transfer (ICT) and blocks the ligand to the metal charge transfer transition (LMCT) process. The intermolecular interactions were quantitatively analyzed by Hirshfeld surface analyses. [ABSTRACT FROM AUTHOR]

A new pyridine-decorated half-salamo-like ligand (HL) was designed and synthesized. Three novel anion-dependent Cu(II) complexes [Cu(L)Cl]·CH 3 OH (1), [Cu(L)Br] (2) and [Cu(L)(NO 3)] (3) have been synthesized and characterized structurally. Furthermore, DFT calculations were investigated in the complexes 1 , 2 and 3. Paradoxically, the fluorescence intensities of these Cu(II) complexes are significantly increased compared to the ligand. [Display omitted] • A new pyridine-decorated half-salamo-like ligand was synthesized. • Three anion-dependent Cu(II) complexes 1 , 2 and 3 have been synthesized and characterized structurally. • The fluorescence intensities of these Cu(II) complexes are significantly increased compared to the ligand. A new pyridine-decorated half-salamo-like ligand (HL) was designed and synthesized by a one-pot method. Based on this ligand, the single crystals of three anion-dependent Cu(II) complexes [Cu(L)Cl]·CH 3 OH (1), [Cu(L)Br] (2) and [Cu(L)(NO 3)] (3) have been cultivated successfully and the structural features were determined by single crystal X-ray diffraction analyses. The results showed that the complexes 1 , 2 and 3 have homologous mononuclear structures, in which the five-coordinated Cu(II) atom is not only surrounded by the N 3 O cavity of the ligand (L)- unit, but also coordinated with Cl−, Br− and NO 3 − as auxiliary coordination, respectively. The ligand HL and the complexes 1 , 2 and 3 were characterized via elemental analyses, IR and UV–Vis spectroscopy. The short-range interactions of the complexes 1 , 2 and 3 were investigated by Hirshfeld surfaces analyses. Furthermore, DFT calculations were investigated in the complexes 1 , 2 and 3. Paradoxically, the fluorescence intensities of these Cu(II) complexes are significantly increased compared to the ligand. [ABSTRACT FROM AUTHOR]

Three trinuclear complexes 1 - 3 possessed inversion centers have been successfully synthesized by wet-chemical method using asymmetric salamo-based polydentate chelating ligand (H 2 L) with Co(OAc) 2 ·4H 2 O and Ni(OAc) 2 ·4H 2 O, respectively. [Display omitted] Three trinuclear complexes, [{CoL(MeOH)(μ -OAc)} 2 Co] (1), [{CoL(EtOH)(μ -OAc)} 2 Co]·2CH 3 CH 2 OH (2) and [{NiL(MeOH)(μ -OAc)} 2 Ni]·2CH 3 OH (3) have been successfully synthesized by wet-chemical method using asymmetric salamo-based polydentate chelating ligand (H 2 L) with transition metal(II) acetate (Co(OAc) 2 ·4H 2 O or Ni(OAc) 2 ·4H 2 O). The ligand H 2 L with N 2 O 2 coordination cavity can accommodate transition metals, at the same time, the oxygen atoms of the phenolic hydroxyl groups can bridge the metal atoms to obtain muiltnuclear metal complexes. There are inversion centers in complexes 1 – 3 and all M(II) atoms possess six-coordinated distorted octahedral geometries. Complexes 1 and 3 are further assembled into extended two-dimensional supramolecular via intermolecular interactions, but complex 2 forms three-dimensional supramolecular structure. The interactions were quantitatively determined by Hirshfeld surfaces analyses. Significantly, complexes 1 – 3 have been characterized by elemental analyses, IR spectra, UV–Vis spectroscopy and X-ray crystallography analyses. Fluorescence properties were also investigated. [ABSTRACT FROM AUTHOR]