Jian‐Min Dou

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.

Antisolvent diffusion-induced growth, equilibrium behaviours in aqueous solution and optical properties of CH3NH3PbI3 single crystals for photovoltaic applications

Crystallization and decomposition of organolead trihalide perovskites (OTPs) are very sensitive to the presence of water in precursor or in ambient conditions. Thus, understanding equilibrium behaviours (crystallization and decomposition) of OTPs in aqueous solution is very critical for OTP solar cells fabricated with water-based precursor solutions. Here, equilibrium behaviours in an aqueous solution of CH3NH3PbI3 (MAPbI3) single crystals (MSCs) were studied. Diethyl ether, as an antisolvent, effectively diffused and induced MSC growth by screening different solvents (diethyl ether, tetrahydrofuran, dichloromethane, and chloroform). The structure transforms from the initial PbI2 to intermediate (HxPbI2+x·xH2O) and finally MSCs were observed by X-ray diffraction. Decomposition of MSCs in aqueous solution was significantly enhanced by potassium iodide coordination and inhibited by CH3NH3I (MAI) addition. We ascribed this inhibition behaviour to suppressing MAI migration from the MSC crystal structure. Finally, the optical properties of MSC were studied.

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.

Theoretical design and screening of alkyne bridged triphenyl zinc porphyrins as sensitizer candidates for dye-sensitized solar cells

Alkyne bridged porphyrins have been proved very promising sensitizers for dye-sensitized solar cells (DSSCs) with the highest photo-to-electric conversion efficiencies of 11.9% solely and 12.3% co-sensitized with other sensitizers achieved. Developing better porphyrin sensitizers with wider electronic absorption spectra to further improve the efficiencies of corresponding solar cells is still of great significance for the application of DSSCs. A series of triphenyl zinc porphyrins (ZnTriPP) differing in the nature of a pendant acceptor group and the conjugated bridge between the porphyrin nucleus and the acceptor unit were modeled and their electronic and spectral properties calculated using density functional theory. As compared with each other and the experimental results of the compounds used in DSSCs previously, the molecules with a relatively longer conjugative linker and a strong electron-withdrawing group such as cyanide adjacent to the carboxyl acid group seem to provide wider electronic absorption spectra and higher photo-to-electric conversion efficiencies. The dye candidates ZnTriPPE, ZnTriPPM, ZnTriPPQ, ZnTriPPR and ZnTriPPS designed in the current work were found promising to provide comparable photo-to-electric conversion efficiencies to the record 11.9% of the alkyne bridged porphyrin sensitizer YD2-o-C8 reported previously.

Theoretical screening of novel alkyne bridged zinc porphyrins as sensitizer candidates for dye-sensitized solar cells

Alkyne bridged porphyrin sensitizers have attracted great attention in the field of dye-sensitized solar cells (DSSCs) because of their excellent photo-to-electric conversion efficiencies, among which YD2 has reached 11% while YD2-o-C8 has reached 11.9% solely and 12.3% co-sensitized with other sensitizers. Design and screening of porphyrin sensitizer candidates with wider electronic absorption spectra to further improve the photo-to-electric conversion efficiencies of corresponding solar cells is still very important. Twenty novel alkyne bridged zinc porphyrin sensitizer candidates composed of the donors diarylamino-, tri-4-methylphenyl-, tri-hydroxyl- and tri-amino-substituted zinc porphyrins as well as the selected acceptors E, M, Q, R and S have been designed and calculated at the density functional B3LYP level. YD2 and YD2-o-C8 are also calculated at the same level for comparison. The result shows that the sensitizer candidates all have smaller HOMO-LUMO gaps as well as wider and red-shifted absorption bands than those of YD2 and YD2-o-C8. Most of the sensitizer candidates have appropriate HOMO and LUMO energy levels relative to the redox potential of the mediator and the TiO2 conduction band, showing that they are promising to provide comparable or even higher photo-to-electric conversion efficiencies than 11% of YD-2 or 11.9% of YD2-o-C8.

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] (mntu2009=u2009maleonitriledithiolate) using different molar ratios (2u2009:u20091 and 4u2009:u20091) 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.

catena‐Poly[[aqua­(cis‐syn‐cis‐dicyclo­hexyl‐18‐crown‐6)lead(II)]‐μ‐thio­cyanato‐κ2N:S‐[dithio­cyanato­palladium(II)]‐μ‐thio­cyanato‐κ2S:N]

The title polymeric complex, [PbPd(NCS)4(C20H36O6)(H2O)]n or {[Pb(DC18C6-A)(H2O)][Pd(SCN)4]}n (DC18C6-A = cis-syn-cis-dicycloxadhexyl-18-crown-6), has been synthesized by the reaction of dicycloxadhexyl-18-crown-6 with PdCl2 and Pb(SCN)2. The SCN groups bridge [Pb(DC18C6-A)(H2O)]2+ complex cations and [Pd(SCN)4]2− complex anions to form infinite polymeric chains.

1,1-Diaqua-2,3,4,5,6-penta­isoprop­oxy-1-nickeladodeca­borane

The title mononickeladodecaxadborane cluster, [NiB11H6(OC3H7)5(H2O)2], has been synthesized by the reaction of dichloroxadbis(triphenylxadphosphine)nickel(II) with triethylxadammonium nido-undecaxadborane(14) in 2-propanol. The NiIV atom is connected to five atoms of the boron cage to form a closo 12-vertex {NiB11} icosaxadhedral skeleton. All of the H atoms on the five B cage atoms connected to the Ni atom are substituted by isopropxadoxy groups. The NiIV atom is also bonded to two water molxadecules. The molxadecules form dimers through interxadmolecular hydrogen-bond interxadactions.

Di-μ-acetato-κ4O:O′-bis­[bis­(2,2′-bipyridine-κ2N,N′)manganese(II)] bis­(perchlorate)

In the binuclear title manganese(II) complex, [Mn2(C2H3O2)2(C10H8N2)4](ClO4)2, the Mn atoms are six-coordinate in a distorted octaxadhedral coordination geometry. The two Mn atoms are bridged by two acetate groups to form a dimeric cation. The complex forms chains through π–π stacking interxadactions.