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In this paper, the boron‐modified polyferrocenylcarbosilanes (namely HBPFCS‐Bs) with hyperbranched structure, as single‐source‐precursors, were successfully prepared by using 9‐borabicyclo [3, 3, 1] nonane (9‐BBN) and polyferrocenylcarbosilanes (HBPFCSs) as starting materials. The obtained HBPFCS‐Bs were characterized using Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC), providing that the boron element can be introduced into the HBPFCS chains by the hydroboration (B‐H/C = C) reaction. Then, the structural evolution of HBPFCS‐Bs and the boron‐containing SiFeC ceramics at different temperatures (1100–1500°C) was further investigated by thermogravimetric analysis, X‐ray diffraction, energy dispersive spectroscopy, scanning electron microscope, and transmission electron microscopy. The results show that the incorporation of a small amount of boron (1 wt%) into precursors significantly improves the properties of the final ceramics, including the significant increase of the ceramic yield, enhanced high‐temperature resistance, as well as the higher ceramic densification. Finally, the saturation magnetization of the HBPFCS‐Bs‐derived ceramics was also enhanced by the introduction of boron. [ABSTRACT FROM AUTHOR]

A new molecular solid [3BrBzTPP]2[Cu(mnt)2](1) (mnt2- D maleonitriledithiolate; [3BrBzTPP]+ D1-(3'-bromobenzyl)triphenylphosphonium) was synthesized and characterized by elemental analysis, optical spectra, and thermal and X-ray crystallographic analyses. It was crystallized in the monoclinic space group P21/n, and the asymmetric unit cell contained half a [Cu(mnt)2]2- anion and one independent [3BrBzTPP]C cation. The anions and cations in 1 were linked by electrostatic interactions, C-H...S hydrogen bonds, and short N...Br interactions, and formed an alternating column of anions and cations in a ¢¢¢AA-CC-AA-CC¢¢¢ sequence. The thermal analysis revealed that 1 was stable up to 218°C. Magnetic measurements disclosed that 1 was a paramagnetic system with a very weak ferromagnetic coupling interaction in the temperature range of 2.0-300 K. [ABSTRACT FROM AUTHOR]

Two new organic-inorganic hybrid materials, [(Ph) 2 CHTPP][Ni(mnt) 2 ]( 1 ) and [(Ph) 2 CHTPP] 2 [Cu(mnt) 2 ]·2CH 3 CN( 2 ) (mnt = maleonitriledithilate, [(Ph) 2 CHTPP] + = diphenylmethane-triphenylphosphinium), were prepared and characterized. Two compounds crystallize in the triclinic lattice with P -1 space group, and the adjoined anions form one-dimension chain structure through weak π⋯π or C⋯N interactions in 1 , and C H⋯S and C H⋯N hydrogen bonds through the solvent lattice acetonitrile molecule in 2 . The power X-ray diffraction patterns are in good agreement with the simulated patterns based on the crystal structures, indicating the purity of the as-grow crystals. FT-IR and UV–vis spectra were recorded and analyzed with the aid of the DFT calculation. The HOMO/SOMO and LUMO energy gaps were calculated by the DFT method explain charge transfer interactions take place within two materials. Thermal analysis shows two materials can be stable up to 171 °C for 1 and 215 °C for 2 . The variable-temperature susceptibility analysis shows that 1 is the para-magnetic system with a spin-gap at 110 K and 2 exhibits a weak antiferromagnetic exchange interaction as the temperature is lowered. [ABSTRACT FROM AUTHOR]

A new salt, [2ClBz2NH2Py][Ni(mnt)2](1), ([2ClBz2NH2Py]+= 1-(2´-chlorobenzyl)-2-aminopyridinium, mnt2−= maleonitril-edithiolate), was prepared and characterized structurally by means of CHN elemental analyses, IR, MS spectra and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space groupC2/cwith lattice contentsa= 24.947(2) Å,b= 12.658(1) Å,c= 15.045(2) Å, β = 97.41(1)°,V= 4711.0(8) Å3, andZ= 8. The Ni(III) ions of 1 form a 1D spiral zigzag non-uniform magnetic chain within a [Ni(mnt)2]−column with the Ni···Ni distances of 3.971 and 4.386 Å, whereas two neighboring [2ClBz2NH2Py]+cations from a dimer by the short Cl···Cl interaction with a distance of 3.585 Å. The cations and anions are linked by N···π, S···π interactions and C-H···N, C-H···S hydrogen bonds. Magnetic susceptibility measurements in the temperature range 2–300 K show that the salt shows characteristic of spin-gap with Δ/kb= 789.1 K. [ABSTRACT FROM AUTHOR]

Two new salts [4-ClBzPid]2[Ni(mnt)2](1) and [4-ClBzPid][Ni(mnt)2](2)([4-ClBzPid]+= 1-(4′-chlorobenzyl)-piperidinium and mnt2−= maleonitriledithiolate) were synthesized and characterized by elemental analyses, IR, UV-Vis, ESI-MS, single crystal X-ray diffraction, and magnetic measurements. The [Ni(mnt)2]2−anions of1form a one-dimensional side-by-side structure via N···N short interaction, whereas the [Ni(mnt)2]−anions in2form a one-dimensional face-to-face column through short inter-molecular Ni···Ni, Ni···S, and S···S interactions in which the Ni(III) ions form a nonuniform magnetic chain with the Ni···Ni distances of 3.676 Å and 4.357 Å. Furthermore, the [4-ClBzPid]+cations in1stack into 1D columns via C–H···Cl and Cl···Cl interactions, while the cations (C) and [Ni(mnt)2]−anions (A) of2stack into a 1D column with a A-CC-A-CC-A sequence by N···π and N–H···N weak interactions. Some other weak interactions including C–H···N and C–H···Ni hydrogen bonds result in the forming of a 3D network. Magnetic susceptibility measurements in the temperature range 2 to 300 K show that two salts exhibit diamagnetic behavior. [ABSTRACT FROM PUBLISHER]

Two new complexes of tetra(isothiocyanate)cobalt(II) dianion and meta-substituted benzyl triphenylphosphinium, [3BrBzTPP]2[Co(NCS)4] (1) and [3CNBzTPP]2[Co(NCS)4] (2) ([3BrBzTPP]+= 1-(3′-bromobenzyltriphenylphosphonium and [3CNBzTPP]+= 1-(3′-cyanobenzyltriphenylphosphonium), were prepared and characterized by elemental analysis, FT–IR, UV-vis spectra, ESI-MS, and single-crystal X-ray diffraction method. Both 1 and 2 crystallize in monoclinicP2(1)/c, and the Co(II) ion of the [Co(NCS)4]2−anion shows a distorted tetrahedral coordination geometry. The C-H···S hydrogen bonds and p···π interaction found in 1 and 2 consolidate the stacking of the crystal. Magnetic susceptibility measurement in the temperature range 2–300 K shows that 1 and 2 exhibit a weak antiferromagnetic coupling behavior. [ABSTRACT FROM PUBLISHER]

In two new bis(maleonitriledithiolate)copper(II) salts, [Bz-1-MeIm]2[Cu(mnt)2] (1) and [4-NO2Bz-1-MeIm]2[Cu(mnt)2] (2) ([Bz-1-MeIm]+= Bz-1-MeMz = 1-methyl-3-benzylimidazolium; [4-NO2Bz-1-MeIm]+= 1-methyl-3-(4′-nitrobenzyl)imidazolium), 1 crystallizes in the triclinic system with space groupP-1, whereas 2 crystallizes in the monoclinic system with space groupP21/c. The cations and anions stack alternately into a column by π···π and C‒H···π interactions, and the C‒H···N and C‒H···O hydrogen bonds consolidate the crystal packing and give further rise to a 3D network structure. Magnetic susceptibility measurements show that 1 displays strong antiferromagnetic interaction withθ= –255.98 K, whereas 2 shows weak ferromagnetic coupling withθ= 0.527 K. [ABSTRACT FROM PUBLISHER]

A new inorganic–organic hybrid material, [EtdiPy][Co(NCS)4] (1) ([EtdiPy]2+ = 1,1′-ethylene-2,2′-dipyridinium), was synthesized and characterized by elemental analysis, IR spectrum, UV-Vis spectrum, ESI-MS, and single-crystal X-ray diffraction. Compound 1 is monoclinic, space group P21/n, with a = 21.691(5) Å, b = 8.639(2) Å, c = 21.748(5) Å, β = 90.124(3)°, V = 4075.1(16) Å, Dc = 1.550 g cm, Z = 8, F(000) = 1928, and R1 = 0.0435. The C–H···S hydrogen bond, short S···C, S···N interactions, p···π, and π···π interactions observed in the solid state of 1 give a 3-D structure. Magnetic measurements from 2 to 300 K have shown weak antiferromagnetic exchange with θ = −0.892 K in 1. [ABSTRACT FROM AUTHOR]

Two new tetrachloromanganate(II) salts, [BzTPP]2[MnCl4] (1) and [4NO2BzTPP]2[MnCl4] (2) ([BzTPP]+ = 1-benzyl- triphenylphosphonium; [4NO2BzTPP]+ = 1-(4′-nitrobenzyl) triphenylphosphonium), have been prepared and characterized. Compound 1 crystallizes in the triclinic space group P-1, while 2 is monoclinic P21/c. Both 1 and 2 comprise one [MnCl4]2− anion and two cations, and the [MnCl4]2− anion exhibits distorted tetrahedral coordination geometry. The cations of 1 form a dimer through C-H···π hydrogen bonds and π···π stacking interactions. The C-H···Cl and C-H···O hydrogen bonds result in a complicated hydrogen-bonded network. Magnetic susceptibility measurements in the temperature range 2–300 K show that both 1 and 2 exhibit very weak antiferromagnetic coupling behavior. [ABSTRACT FROM PUBLISHER]

Two new tetrachlorocobaltate(II) salts, [BzTPP]2[CoCl4]·H2O (1) and [4NO2BzTPP]2[CoCl4]·H2O (2) ([BzTPP]+ = 1-benzyl- triphenylphosphonium; [4NO2BzTPP]+ = 1-(4′-nitrobenzyl)tri- phenylphosphonium), have been prepared and characterized by elemental analysis, IR, MS, single-crystal X-ray diffraction, and magnetic susceptibility. Both 1 and 2 crystallize in the monoclinic space group P21/c. The [CoCl4]2− anion exhibits a distorted tetrahedral coordination geometry. The C-H···Cl, C-H···O, and C-H···π hydrogen bonds in 1 and 2 give rise to a 3D hydrogen-bonded network structure. Magnetic susceptibility measurements in the temperature range 2–300 K show that both 1 and 2 exhibit an antiferromagnetic coupling behavior. [ABSTRACT FROM PUBLISHER]

Two new tetrachlorocuprate(II) salts, [BzDMAP]2[CuCl4](1) and [4FBzDMAP]2[CuCl4](2) ([BzDMAP]+ = 1-benzyl-4-dimethylaminopyridinium; [4FBzDMAP]+ = 1-(4′-fluorobenzyl)-4-dimethylaminopyridinium), have been prepared and characterized by elemental analysis, IR, MS, single-crystal X-ray diffraction and magnetic susceptibility. Compound 1 crystallizes in the monoclinic system with space group P21/n, while 2 crystallizes in the orthorhombic system with space group P212121. These two salts comprise one [CuCl4]2– anion and two cations, and the [CuCl4]2– anions exhibit distorted tetrahedral coordination geometry. The C˭H···Cl, C˭H···π hydrogen bonds and π···π stacking interactions in the crystal play important roles in the stacking and stabilization of the two salts, and give rise to a 3D network structure. Magnetic susceptibility measurements in the temperature range of 2–300 K show that both 1 and 2 exhibit a ferromagnetic coupling behavior. [ABSTRACT FROM PUBLISHER]

A new salt, [NO2BzDMAP]3[Cu2Cl7] · H2O (1), has been synthesized, where [NO2BzDMAP]+ is 1-(4′-nitrobenzyl)-4-dimethylaminopyridinium. Herein, the synthesis, spectral and structural characterization, and magnetic behavior of 1 are reported. It is orthorhombic, with space group Pca21, and a = 26.639(2) Å, b = 9.638(1) Å, and c = 20.011(2) Å with V = 5137.5(7) Å3 for Z = 4. The anion shows a chloride-bridged binuclear structure with Cu ··· Cu distance of 3.872 Å; the two Cu(II) ions have a tetrahedral geometry. The cations stack through p ··· π and π ··· π interactions, and a complicated hydrogen-bonding network structure is formed through C–H ··· Cl and C–H ··· O hydrogen bonds. The variable temperature magnetic susceptibility measurements reveal that 1 exhibits strong antiferromagnetic interaction with J = −193.0 cm−1. [ABSTRACT FROM AUTHOR]

Abstract: A novel molecular solid, [OFBzIQl][Ni(mnt)2] (1), where [OFBzIQl]+ =1-(2′-fluorobenzyl)isoquinolinium and mnt2− =maleonitriledithiolate, forms 1D column of alternating between cations and anions via π⋯π stacking interaction between Ni(mnt)2 plane and isoquinoline ring, and the Ni(mnt)2 anions between the adjacent columns exist short C⋯N interaction. The extensive hydrogen bonds between anions and cations in the crystal generate a 2D network structure. Magnetic susceptibility measurement for 1 in the temperature range 2.0–300K shows that 1 exhibits a magnetic constant transition from ferromagnetic to antiferromagnetic around 35K as the temperature is lowered. [Copyright &y& Elsevier]

Abstract: The preparation, crystal structures and magnetic properties of two novel salts, [DiBzPid][Ni(mnt)2](1) and [DiBzPid]2[Cu(mnt)2](2), where [DiBzPid]+ = N,N′-dibenzylpiperidinium and mnt2− =maleonitriledithiolate, are investigated. The Ni(III) ions of 1 form a 1D zigzag alternating chain in a [Ni(mnt)2]− column through intermolecular π⋯π stacking interaction, short C⋯S and C⋯N interactions between the adjacent anions, while the cations(C) and anions(A) of 2 stack into a 1D alternating ⋯CCACCACC⋯ column via C–H⋯N, C–H⋯π hydrogen bonds and π⋯π stacking interactions. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 exhibits a spin-gap transition around 150K with Δ/kb =429.94K, while 2 shows a very weakly ferromagnetic coupling behavior with θ =1.18×10−2 K. [Copyright &y& Elsevier]

Three new ion–pair complexes, [2-ClBz-2′-NH 2 Py] 2 [Cu(mnt) 2 ]( 1 ), [2-Cl-4-ClBz-2-NH 2 Py] 2 [Cu(mnt) 2 ]( 2 ) and [2-Cl-4-BrBz-2′-NH 2 Py] 2 [Cu(mnt) 2 ]·C 2 H 5 OH( 3 ) ([2-Cl-4-RBz-2′-NH 2 Py] + = 1-(2′-chloro-4′-Rbenzyl)-2-aminopyridinium, R = H, Cl, Br; mnt 2− = maleonitriledithiolate), were synthesized and characterized by elemental analyses, IR, UV–visible, single crystal X−ray diffraction and magnetic measurements. Both 1 and 2 crystallize in the monoclinic space group P 2(1)/ c , and the [Cu(mnt) 2 ] 2− anions and the cations form a 1D network structure through the N–H⋅⋅⋅N hydrogen bonds. While the anions in 3 form a ladder-like chain through the C–H⋅⋅⋅N interactions between the [Cu(mnt) 2 ] 2− anions and CH 3 CH 2 OH molecules. Some weak interactions such as π⋅⋅⋅π, Cu⋅⋅⋅N, Cl⋅⋅⋅C, and C–H⋅⋅⋅Cl, O–H⋅⋅⋅Cl, C–H⋅⋅⋅S, N–H⋅⋅⋅O, N–H⋅⋅⋅N and C–H⋅⋅⋅N hydrogen bonds in three molecular solids generate further a 3D network structure. The magnetic measurement reveals that 1 shows a very weak ferromagnetic interaction, and 2 exhibits a transition from ferromagnetic to antiferromagnetic coupling about 15 K, while 3 shows an antiferromagnetic coupling feature with θ = −12.51 K when the temperature is lowered. [ABSTRACT FROM AUTHOR]

Two new organic–inorganic molecular solids of tetra(isothiocyanate)cobalt(II) dianion and disubstituted benzyl triphenylphosphinium, [2Cl4FBzTPP] 2 [Co(NCS) 4 ] ( 1 ) and [2Cl4ClBzTPP] 2 [Co(NCS) 4 ] ( 2 ) ([2Cl4FBzTPP] + = 1-(2′-chloro-4′-fluorobenzyltriphenylphosphonium) and [2Cl4ClBzTPP] + = 1-(2′,4′-dichlorobenzyltriphenylphosphonium), were synthesized and characterized by elemental analysis, FT-IR, UV–Vis spectra, ESI-MS and single crystal X-ray diffraction method. Compounds 1 and 2 crystallize in the monoclinic Pc and triclinic P -1, respectively. The Co(II) ion of the [Co(NCS) 4 ] 2− anion shows a distorted tetrahedral coordination geometry. The [2Cl4FBzTPP] + cations containing P(2) atoms in 1 form a column by the Cl⋯π interactions, while the [2Cl4ClBzTPP] + cations in 2 form two columns by the C–H⋯π and π⋯π interactions. The anion and the cation are linked by C–H⋯S hydrogen bonds and Cl⋯S interactions. Magnetic susceptibility measurement in the temperature range 2–300 K shows that both 1 and 2 exhibit a weak antiferromagnetic exchange interaction as the temperature falls, and ultraviolet fluorescence emission in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

The reaction of CoCl 2 with the naphthalene methylated triphenylphosphinium bromide [ n -NAPMeTPP]Br ( n = 1, 2) and KSCN, in a methanolic medium at ambient temperature, leads to the self-assembly formation of hybrid 2:1 organic–inorganic molecular solids, [1-NAPMeTPP] 2 [Co(NCS) 4 ]( 1 ) and [2-NAPMeTPP] 2 [Co(NCS) 4 ]( 2 ) ([NAPMeTPP] + = (naphthylmethylene)(triphenyl)phosphinium), which have been characterized by elemental analyses, IR spectroscopy, UV–Vis spectra, ESI-MS, molar conductivity and single-crystal X-ray diffraction structural analyses. Compound 1 crystallizes in the orthorhombic space group Pna 2 1 , while 2 does in the monoclinic space group C 2/ c . The cations form a dimer through the weak intermolecular C–H⋯π interactions in 1 and π⋯π interaction in 2 , while the anion and cation are linked by the C–H⋯S hydrogen bond in 1 . Two molecular solids show dual functionalities: (1) the broad fluorescence emission around 400 nm in the solid state at room temperature; (2) the weak antiferromagnetic coupling behavior. [ABSTRACT FROM AUTHOR]

Two new molecular solids, [4FBzIQl][Ni(mnt) 2 ]( 1 ) and [4FBzIQl] 2 [Cu(mnt) 2 ]( 2 ) ([4FBzIQl] + = [1-(4′-fluorobenzyl)isoquinolinium; mnt 2− = maleonitriledithiolate) have been obtained by complexing of the [M(mnt) 2 ] n − (M = Ni(III) or Cu(II), n = 1 or 2) anion with [4FBzIQl] + cation. Single-crystal structural analysis reveals that both molecular metals crystallize in the triclinic space group P -1. The [Ni(mnt) 2 ] − anions of 1 form a column by short C⋯N and C⋯C interactions between the cyano groups of the anions, while two adjacent [Cu(mnt) 2 ] 2− anions of 2 form a dimer through S⋯S interaction. The neighboring cations form a dimer or 2D layered structure through C H⋯F hydrogen bonds, F⋯F interactions, and π ⋯ π stack interactions. The anions and cations stack alternately into a 1D column through C H⋯N, π ⋯ π or/and C H⋯S, C HCu interactions. Magnetic susceptibility measurements in the temperature range 2–300 K reveal that 1 exhibits a characteristic of two spin-gaps around 103.8 K and 7.5 K, respectively, while 2 shows a change of magnetic exchange from weak ferromagnetic to antiferromagnetic interaction around 43.9 K when the temperature is lowered. [ABSTRACT FROM AUTHOR]

Two new organic–inorganic molecular solids of tetra(isothiocyanate)cobalt(II) dianion and meta-substituted benzyl triphenylphosphinium, [2ClBzTPP] 2 [Co(NCS) 4 ] ( 1 ) and [4ClBzTPP] 2 [Co(NCS) 4 ] ( 2 ) ([2ClBzTPP] + = 1-(2′-chlorobenzyltriphenylphosphonium) and [4ClBzTPP] + = 1-(4′-chlorobenzyltriphenylphosphonium), were prepared and characterized by elemental analysis, FT-IR, UV–vis spectra, ESI-MS and single crystal X-ray diffraction method. Both 1 and 2 crystallize in monoclinic, and the Co(II) ion of the [Co(NCS) 4 ] 2− anion shows a distorted tetrahedral coordination geometry. The C H⋯Cl, C H⋯S hydrogen bonds were found in 1 while C H⋯S, C H⋯Co, p⋯π, C H⋯π interactions were found in 2 consolidating the stacking of the crystal. Magnetic susceptibility measurement in the temperature range 2–300 K shows that 1 and 2 exhibit a weak antiferromagnetic coupling behavior. Upon excitation at 268 nm, two molecular solids show the luminescent emission peak in the UV-light region in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

Three molecular solids, [2RBzIQl] 2 [Cu(mnt) 2 ] (mnt 2− = maleonitriledithiolate; [2RBzIQl] + = 1-(2′-R-benzyl) isoquinolinium, R = F( 1 ), Cl( 2 ) and Br( 3 )), have been prepared and systemically investigated. The crystal structural analysis reveals that three molecular metals crystallize in the monoclinic with space group P 2 1 / c , and the [2RBzIQl] + cations stack into an one-dimensional column through C H⋯π, π⋯π and C H⋯X (X = F or Cl) interactions while the [Cu(mnt) 2 ] 2− anions in 1 and 2 form a dimer by the side-to-side S⋯S, N⋯N and S⋯N interactions. The anions (A) and cations (C) are arranged alternatively into one 1D column for 1 and 2 and two 1D columns for 3 with a ⋯A CC A CC A⋯ sequence though C H⋯S, C H⋯π, C H⋯N or/and C H⋯Cu hydrogen bonds, and weak X⋯N (X = F, Cl), Br⋯S, Cu⋯N or/and π⋯π interactions. The magnetic susceptibilities measured in the temperature range 2.0–300 K reveal that 1 shows an antiferromagnetic behavior, while 2 and 3 exhibit a change of magnetic exchange from weak ferromagnetic to antiferromagnetic around 48 K upon the temperature is lowered. [ABSTRACT FROM AUTHOR]

Two molecular metals, [2F4BrBzTPP][Ni(mnt) 2 ]·H 2 O ( 1 ) and [2Br4FBzTPP][Ni(mnt) 2 ] ( 2 ) ([2F4BrBzTPP] + = 1-(2′-fluoro-4′-bromobenzyltriphenylphosphonium, [2Br4FBzTPP] + = 1-(2′-bromo-4′-fluorobenzyltriphenylphosphonium, mnt 2− = maleonitriledithiolate), have been synthesized and structurally characterized by single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic space group P −1, while 2 does in the monoclinic space group P 2 1 / c . The Ni(III) ions from [Ni(mnt) 2 ] − anion of 1 form a 1D non-uniform chain through Ni⋯S, Ni⋯Ni and π⋯π interactions with the Ni⋯Ni distances of 3.443, 3.935 and 3.968 Å, as well as C H⋯F, C H⋯N, C H⋯π, and π⋯π weak interactions exist in 1 . The anions and cations in 2 stack into segregated structure, and the anions give rise to a 1D uniform column with a Ni⋯Ni distance of 4.148 Å. Magnetic measurements have shown that 1 exhibits a characteristic of spin-gap ( Δ / k b = 267.5 K) around 86 K, while 2 shows an antiferromagnetic coupling feature with J = −15.4 cm −1 upon the temperature is lowed. [ABSTRACT FROM AUTHOR]

Syntheses, crystal structures and magnetic properties of three molecular solids, [2RBzTPP] 2 [Cu(mnt) 2 ] (mnt 2− = maleonitriledithiolate; [2RBzTPP] + = 1-(2′-R-benzyl)triphenylphosphonium, R = F( 1 ), Cl( 2 ) and Br( 3 )) are investigated. All three molecular metals crystallize in the triclinic space group P -1. The change of the molecular topology of the counteraction when the o -substituted group in the benzyl ring has changed from F to Cl and Br, results in the difference in the dihedral angles, the stacking mode and the weak interactions of the cations and anions of 1 , 2 and 3 . The effect of weak intramolecular interactions such as C H⋯X(X = F, Cl, Br), C H⋯S, C H⋯N, C H⋯Cu, C H⋯π hydrogen bonds and the short X⋯X interactions generates a 3D network structure. The magnetic susceptibilities of these molecular metals measured in the temperature range 2.0–300 K show that the overall magnetic behaviors of 1 – 3 correspond to a paramagnetic system with a very weak ferromagnetic coupling interaction with θ = 0.013 K for 1 , 0.019 K for 2 and 0.025 K for 3 . [ABSTRACT FROM AUTHOR]

Highlights: [•] Crystal structures of three molecular metals were obtained. [•] The Ni(III) ions of 1 form a non-uniform 1D magnetic chain. [•] The Ni(III) ions of 2 form a 1D uniform chain. [•] The [Ni(mnt)2]− anions of 3 show a stepwise structure. [•] Three molecular metals exhibit an interesting characteristic of spin-gap. [ABSTRACT FROM AUTHOR]

Highlights: [•] Three one-dimensional molecular metals were achieved. [•] The Ni(III) ions of 1–3 form a non-uniform 1D magnetic chain. [•] Compound 1 exhibits an interesting characteristic of spin-gap. [•] Compounds 2 and 3 show a very strong antiferromagnetic coupling feature. [ABSTRACT FROM AUTHOR]

Highlights: [•] Four molecular solids containing [Cu(mnt)2]2−/[Ni(mnt)2]− anion were synthesized and characterized. [•] There are F⋯F, Cl⋯Cl and C–H⋯Cu anagostic interactions in 1 and 2. [•] The Ni(III) ions in a [Ni(mnt)2]− column of 3 and 4 form a 1D linear chain. [•] Compound 1 and 2 show weak ferromagnetic coupling at 20–300K. [•] Compound 3 and 4 exhibit characteristic of antiferromagnetic coupling. [ABSTRACT FROM AUTHOR]

Abstract: Two new ion-pair complexes, [ClBrBzPyN(CH3)2]2[Cu(mnt)2](1) and [ClBrBzPyN(CH3)2][Ni(mnt)2](2) have been obtained by self-assembly of the [M(mnt)2] x− (M=Cu(II) or Ni(III), mnt2− =maleonitriledithiolate, x =1 or 2) anion and [ClBrBzPyN(CH3)2]+ ([ClBrBzPyN(CH3)2]+ =[1-(4′-chloro-2′-bromobenzyl)-4-dimethylaminopyridinium]) cation. The cations in 1 stack into a column through the CBr hydrogen bonds and the π⋯π stacking interactions, while the [Cu(mnt)2]2− (A) and the cations (C) stack alternately into a 1D column (i.e., of type ⋯CCACCACC⋯). The anions and the cations in 2 stack into segregated columns in which the Ni(III) ions form a uniform 1D zigzag magnetic chain. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 exhibits an antiferromagnetic coupling feature with θ =−25.3K, while 2 shows characteristic of spin-gap (Δ/k b =1044.3K) around 114K. [Copyright &y& Elsevier]

Abstract: The preparation, crystal structures and magnetic properties of two complexes containing bis(maleonitriledithiolate)nickel(III)/copper(II) anion, [4BrBzTPP][Ni(mnt)2] (1) and [4BrBzTPP]2[Cu(mnt)2] (2) ([4BrBzTPP]+ =1-(4′-bromobenzyl)triphenylphosphinium) are report here. The crystals of two complexes belong to the triclinic system with space group P-1. The [Ni(mnt)2]− anions form a stepwise stack for 1 through weak π···π stacking interactions, short C···S interactions between the neighboring anions, while the [Cu(mnt)2]2− anions and the [4BrBzTPP]+ cations in 2 are linked through Ch name="pdbond" />S, Ch name="pdbond" />N and Ch name="pdbond" />Cu hydrogen bonds. The difference of the stacking mode and the weak interactions in 1 and 2 results in the difference of the magnetic properties: complex 1 exhibits an activated magnetic behavior in the high-temperature range together with a Curie tail at lower temperature range, while 2 shows a ferromagnetic exchange interaction with θ =25.65K. [Copyright &y& Elsevier]

Abstract: Two tetrachlorocuprate(II) salts, [4-RBzPy]2CuCl4 ([4-RBzPy]+ =4-R-benzylpyridinium, R=Cl(1), NO2(2)), have been prepared and characterized by elemental analysis, IR, MS, single-crystal X-ray diffraction and magnetic susceptibility. Compound 1 crystallizes in the orthorhombic system with space group Pca21, while 2 in the monoclinic P21/c. Two salts comprise a tetrahedral [CuCl4]2− anion and two flexuous [4-RBzPy]+ cations. The cations both 1 and 2 form a column through p⋯π and π⋯π interactions, while the [CuCl4]2− anions only in 2 form a dimer through Cl⋯Cl interaction. The C–H⋯Cl and C–H⋯Cu weak hydrogen bonds between the anions and the cations give further rise to a 3D network structure. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 exhibits a ferromagnetic coupling behavior with θ =3.57K, while 2 shows an antiferromagnetism with J =−11.09cm−1. [Copyright &y& Elsevier]

Abstract: The self-assembly of [Co(NCS)4]2− anion and substituted benzyltriphenylphosphonium cations [4RBzTPP]+ (R=H(1), NO2(2)) results in the forming of two new hybrid materials, [BzTPP]2[Co(NCS)4](1) and [4NO2BzTPP]2[Co(NCS)4](2). The Co(II) ions of the [Co(NCS)4]2− anions in 1 form a 1D chain through S⋯S interactions with the S⋯S distance of 3.458Å, while the C–H⋯S, C–H⋯O hydrogen bond and p⋯π interaction were found in 2. Magnetic susceptibility measurement in the temperature range 2–300K shows that 1 exhibits a magnetic coupling interaction from ferromagnetic to antiferromagnetic around 30K as the temperature is lowered, while 2 shows weak antiferromagnetic coupling behavior. [ABSTRACT FROM AUTHOR]

Abstract: Three new ion-pair complexes, [4RBzDMAP]2[Cu(mnt)2] (mnt2− =maleonitriledithiolate; [4RBzDMAP]+ =1-(4′-R-benzyl)-4-dimethylaminopyridinium, R=F(1), Cl(2) and Br(3)) were synthesized and characterized by elemental analyses, IR, UV, single crystal X-ray diffraction and magnetic measurements. The [Cu(mnt)2]2− anions and the cations stack alternately and form a 1D column via C–H···S, C–H···π or C–H···Cu interactions for 1 and 2. While the cations stack into a column though π···π or C–H···π interactions between pyridine and phenyl rings for 1 and 3. The change of the molecular topology of the counteraction when the 4-substituted group in the benzyl ring have been changed from F or Cl to Br atom, results in the difference in the crystal system, space group and the stacking mode of the cations and anions of 1, 2 and 3. Some weak hydrogen bonds between the adjacent columns further generate a 3D network structure. It is interesting that 1 and 2 exhibits antiferromagnetic coupling with θ =−2.372K and θ =−14.732K, while 3 shows weak ferromagnetic coupling feature with θ =0.381K. [ABSTRACT FROM AUTHOR]

Abstract: Two new molecular solids, [1-NaMePid][Ni(mnt)2] (1) and [2-NaMePid][Ni(mnt)2] (2) (mnt2− =maleonitriledithiolate, [1-NaMePid]+ =1-(1′-naphthylmethyl)piperidinium and [2-NaMePid]+ =1-(2′-naphthylmethyl)piperidinium) have been characterized structurally and magnetically. Both [Ni(mnt)2]− anions and the cations of 1 and 2 form segregated column stacks, and the Ni(III) ions form a 1D zigzig alternating magnetic chain within a [Ni(mnt)2]− column through Ni···S, S···S, Ni···Ni, or π···π interactions. Some conformational features in two isomeric cations and the geometry of the individual [Ni(mnt)2]− anion for 1 and 2 remain similar, while the changes of the space filling properties, the packing requirements and the existence of the water molecule in 2 result in the difference of the stacking mode of the [Ni(mnt)2]− anions. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 is diamagnetism, while 2 exhibits a novel and interesting spin–gap transition around 16.8K with antiferromagnetic interaction (J =−4.6cm−1) in the high-temperature phase (HT) and the spin–gap (Δ/k b =68.5K) in the low-temperature phase (LT). [Copyright &y& Elsevier]

Abstract: Two new molecular solids, [BzPyNH2][Ni(mnt)2](1) and [2-NpCH2PyNH2][Ni(mnt)2](2) (mnt2− =maleonitriledithiolate, [BzPyNH2]+ =1-benzyl-2-aminopyridinium and [2-NpCH2PyNH2]+ =1-(2′-naphthylmethylene)-2-aminopyridinium) have been characterized structurally and magnetically. The Ni(Ш) ions of 1 and 2 form a 1D magnetic chain within a [Ni(mnt)2]− column through Ni⋯N or π⋯π interactions. Some weak interactions observed in 1 and 2 give further rise to a 2D structure. The overlapping fashions of the [Ni(mnt)2]− anions are different when the 2-aminopyridine ring was fixed and the phenyl ring changed into the naphthyl ring of the cation. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 is weak antiferromagnetic coupling, while 2 exhibits a novel and interesting spin-gap transition around 140K with Δ/kb =381.4K. [Copyright &y& Elsevier]

Abstract: Two new ion-pair complexes, [FBrBzPyN(CH3)2]2[Ni(mnt)2] (1) and [FBrBzPyN(CH3)2][Ni(mnt)2] (2) (mnt2− =maleonitriledithiolate, [FBrBzPyN(CH3)2]+ =[1-(4′-fluoro-2′-bromobenzyl)-4-dimethylaminopyridinium]) have been prepared and characterized by elemental analyses, UV, IR, single crystal X-ray diffraction and magnetic susceptibility. The cations (D) and the anions (A) in 1 stack into a 1D alternating column (i.e., of type ⋯DDADDADD⋯) via short S⋯Br, N⋯F, C⋯N interactions, and C–H⋯Br hydrogen bonds. The cation–cation π⋯π stacking interactions within the columns give further rise to a 2D network structure. Compound 2 forms a 3D structure in which the Ni(III) ions stack into a uniform 1D zigzag magnetic chain through Ni⋯S, Ni⋯Ni, or π⋯π interactions with a Ni⋯Ni distance of 4.024Å. Magnetic susceptibility measurements in the temperature range 2–300K show that 1 is expected to be diamagnetic, and 2 exhibits an interesting spin-gap transition (Δ/kb =460.6K) around 155K. [Copyright &y& Elsevier]

Abstract: Syntheses, structural characterizations, magnetic behaviors and theoretical analyses of two new ion-pair complexes, [IFBzIQl][Ni(mnt)2](1) and [IClBzIQl]2[Ni(mnt)2]2 ·MeCN(2) [IFBzIQl][Ni(mnt)2] ([IFBzIQl]+ =1-(2′-fluoro-4′-iodobenzyl)isoquinolinium, [IClBzIQl]+ =1-(2′-chloro-4′-iodobenzyl)isoquinolinium, mnt2− =maleonitriledithiolate), have been investigated. In crystal of 1, the [Ni(mnt)2]− anions and the [IFBzIQl]+ cations stack into an alternating column through π⋯π stacking interactions. The anions of both 1 and 2 form a dimer via π⋯π stacking and S⋯S short interactions between the [Ni(mnt)2]− anions. The overlapping mode of two neighboring [Ni(mnt)2]− anions in the dimer is the Ni-ring fashion with a Ni⋯Ni distance of 4.076Å for 1, and ring–ring fashion with the Ni⋯Ni and S⋯S distances being 4.395 and 3.593Å for 2. Some weak interactions such as π⋯π, C⋯N, C–H⋯F or C–H⋯N in 1 and 2 play a crucial role in stacking and stabilizing the crystal lattice, and give a 3D network structure and exchange pathways of the magnetic interaction for 1 and 2. Magnetic susceptibility measurements for 1 and 2 in the temperature range 1.8–300K show that the overall magnetic behavior indicates the presence of antiferromagnetic interaction, while 2 exhibits an activated magnetic behavior in the high-temperature region (HT) together with a Curie tail in the low-temperature region (LT). [Copyright &y& Elsevier]