Feng-Ying Dong

Synthesis, Crystal Structure and Electrochemical Properties of 2D Network Complex {[K(N18C6)]2(CH3CN)}[Ni(mnt)2] with N18C6 = 2,3-Naphtho-18-Crown-6

A novel 2D network complex [K(N18C6)]2(CH3CN) [Ni(mnt)2] (1) (where N18C6 = 2,3-naphtho-18-crown-6 and mnt = maleonitriledithiolate) has been synthesized and characterized by elemental analysis, FT-IR spectrum, UV-visible spectrum and single crystal X-ray diffraction. The complex molecules are linked into 1D chains by the bridging CH3CN molecules through weak K-N interactions and the result chains are assembled into a novel 2D network through the inter-chain π–π stacking interactions occurred between adjacent naphthylene moieties of N18C6. The cyclic voltammogram of the title complex displays a reversible process corresponding to the [Ni(mnt)2]−/[Ni(mnt)2]2− reaction.

One- or two-dimensional 2,3-naphtho crown ether complexes [Na(N15C5)]2[M(SCN)4] and [K(N18C6)]2[M(SCN)4] (M = Pd, Pt) constructed by π–π stacking interactions

Four novel 2,3-naphtho-15-crown-5 (N15C5) and 2,3-naphtho-18-crown-6 (N18C6) complexes [Na(N15C5)]2[Pd(SCN)4] (1), [Na(N15C5)]2[Pt(SCN)4] (2), [K(N18C6)]2[Pd(SCN)4] (3) and [K(N18C6)]2[Pt(SCN)4] (4) were synthesized and characterized by elemental analysis, FT-IR spectra and single-crystal X-ray diffraction. The structure analyses reveal that both 1 and 2 are assembled into zigzag chains by the strong intermolecular pi-pi stacking interactions between adjacent 2,3-naphthylene groups of N15C5. The molecules of complexes 3 and 4 are linked into 1D chains by the bridging K-O(ether) interactions between the adjacent [K(N18C6)]+ units and the resulting chains are constructed into a novel 2D network by inter-chain pi-pi stacking interactions between the neighboring 2,3-naphthylene moieties of N18C6. According to the supramolecular self-assemblies of complexes 1-4, two types of stacking model of naphthylene groups are given and discussed.

Unusual coordination features and self-assembly of a crown ether complex [Na2(2,3-naphtho-15-crown-5)2(NO3)][Cu(NO3)3(H2O)]

A novel supramolecular complex, [Na2(2,3-naphtho-15-crown-5)2(NO3)][Cu(NO3)3(H2O)] (1), has been prepared and characterized by X-ray single crystal diffraction. The complex crystallizes in the triclinic system, space group Pī, with a = 11.233(6), b = 13.342(7), c = 16.601(8) Å, α = 89.836(7), β = 79.132(8), γ = 66.545(7)°, V = 2234(2) Å3, Z = 2 and final R 1(wR 2) = 0.0467(0.1164). Novel coordination features and supramolecular architectures are found in the solid state of 1. Two [Na(2,3-naphtho-15-crown-5)]+ cations containing two different sodium coordination numbers (six and seven) are bridged by a tridentate nitrate group, to form a larger complex cation, [Na2(2,3-naphtho-15-crown-5)2(NO3)], which is assembled into a novel 1D zigzag chain-like structure through aromatic C–H ··· π interactions.

Synthesis and Crystal Structure of One‐dimensional cis‐syn‐cis‐dicyclohexyl‐18‐crown‐6 Complexes: [Na(DC18C6‐A)]2[M(mnt)2] (M=Pd, Pt)

Two inorganic‐organic hybrid complexes [Na(DC18C6‐A)]2[Pd(mnt)2] (1), and [Na(DC18C6‐A)]2[Pt(mnt)2] (2) (DC18C6‐A=cis‐syn‐cis‐dicyclohexyl‐18‐crown‐6, isomer A; mnt=maleonitriledithiolate) have been obtained by the reaction of dicyclohexyl‐18‐crown‐6 with Na2mnt and PdCl2 or K2PtCl4. Their compositions and crystal structures are characterized by elementary analysis, FT‐IR, UV‐Vis spectroscopy and x‐ray single crystal diffraction. They both crystallize triclinic, space group P ī with crystallographic data: 1, a=10.283(6) Å, b=11.683(7) Å, c=12.681(8) Å, α=100.566(8)°, β=109.686(7)°, γ=100.733(8)°, V=1358.5(14) Å3, Z=1, Dcalcd=1.440 g/cm3, F(000)=616, R 1=0.0290, wR 2=0.0676. 2, a=10.289(6) Å, b=11.691(7) Å, c=12.679(7) Å, α=100.495(8)°, β=109.762(8)°, γ=100.886(8)°, V=1358.6(14) Å3, Z=1, Dcalcd=1.548 g/cm3, F(000)=648, R 1=0.0325, wR 2=0.0514. The two complexes are isomorphous and both display an infinite 1D chain‐like structure formed by [Na(DC18C6‐A)]+ complex cations and [M(mnt)2]2− (M=Pd, Pt) complex anions through N‐Na‐N interactions, indicating that the difference from Pd and Pt has little influence on the supramolecular assembly of the two complexes.

Novel crystal engineering in the crown ether nickel maleonitriledithiolate complexes, synthesis and crystal structures of [Na(N15C5)2]2[Ni(mnt)2] and [Na(N15C5)]2[Ni(mnt)2]

Reactions of N15C5 (2,3-naphtho-15-crown-5) with nickel maleonitriledithiolate sodium complex, Na2[Ni(mnt)2] (mnt = maleonitriledithiolate) using different molar ratios (2 : 1 and 4 : 1) afforded two structurally different complexes [Na(N15C5)2]2[Ni(mnt)2] (1) and [Na(N15C5)]2[Ni(mnt)2] (2). The sandwich [Na(N15C5)2]+ and mono-capped [Na(N15C5)]+ organic cations are observed in the crystals of 1 and 2, respectively, with the same [Ni(mnt)2]2− inorganic conteranions. It is these structurally different organic cations that lead to the dissimilar structures. Complex 1 exhibits a one-dimensional (1D) chain-like structure assembled by intercantionic {[Na(N15C5)2]+}∞ π–π stacking interactions and electrostatic interactions, while 2 displays a novel two-dimensional (2D) corrugated sheet-like structure constructed by Na–N interactions which occur between the [Na(N15C5)]+ inorganic cations and [Ni(mnt)2]2− inorganic anions.