Shu-Ni Li

Synthesis, Crystal Structures, and Photoluminescent Properties of the Cu(I)/X/α,ω-Bis(benzotriazole)alkane Hybrid Family (X = Cl, Br, I, and CN)

This work focused on a systematic investigation of the influences of the spacer length of the flexible alpha,omega-bis(benzotriazole)alkane ligands and counteranions on the overall molecular architectures of hybrid structures that include Cu(I). Using the self-assembly of CuX (X = Cl, Br, I, or CN) with the five structurally related flexible organic ligands (L1-L5) under hydro(solvo)thermal conditions, we have synthesized and characterized 10 structurally unique materials of the Cu(I)/X/alpha,omega-bis(benzotriazole)alkane organic-inorganic hybrid family, {[CuCl](2)(L1)}(n) (1), {[CuBr](L2)}(n) (2), {[CuCl](2)(L3)}(n) (3), {[CuI](2)(L4)}(n) (4), {[CuBr](2)(L4)}(n) (5), {[CuBr](3)(L5)}(n) (6), {[CuCN](2)(L1)}(n) (7), {[CuCl](4)(L2)}(n) (8), {[CuBr](4)(L2)}(n) (9), and {[CuCl](2)(L4)}(n) (10), by means of elemental analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and photoluminescence measurements. Single-crystal X-ray analyses showed that the inorganic subunits in these compounds were {Cu(2)X(2)} binuclear clusters (1 and 2), {Cu(4)X(4)} cubane clusters (4, 5, and 10), {CuX}(n) single chains (3 and 7), a {Cu(3)X(3)}(n) ladderlike chain (6), and unprecedented {Cu(8)X(8)}(n) ribbons (8 and 9). The increasing dimensionality from 1-D (1-4) to 2-D (5 and 6) to 3-D (7-10) indicates that the spacer length and isomerism of the bis(benzotriazole)alkane ligands play an essential role in the formation of the framework of the Cu(I) hybrid materials. The influence of counteranions and pi-pi stacking interactions on the formation and dimensionality of these hybrid coordination polymers has also been explored. In addition, all the complexes exhibit high thermal stability and strong fluorescence properties in the solid state at ambient temperature.

Solvothermal synthesis, crystal structures and photoluminescence properties of the novel Cd/X/α,ω-bis(benzotriazole)alkane hybrid family (X = Cl, Br and I)

Seven organic-inorganic hybrid solids, namely, [(CdI2)2(L1)2] (1), [(CdBr2)3(L1)2]n (2), [(CdCl2)5(L1)2]n (3), [(CdI2)(L2)]n (4), [(CdBr2)(L3)]n (5), [(CdBr2)2(L4)2]n (6), and [(CdI2)4(L4)4]n (7), have been obtained via the self-assembly of CdX2 (X = Cl, Br or I) with the four structurally related flexible organic ligands 1,2-bis(benzotriazole)ethane (L1), 1,3-bis(benzotriazole)propane (L2), 1,4-bis(benzotriazole)butane (L3) and 1,6-bis(benzotriazole)hexane (L4) under solvothermal conditions. Compound 1 presents a binuclear structure with a [Cd2N12C4] 18-membered cycle. In 2, the L1 ligands locate alternately on the two sides of the 1-D inorganic chain formed by papilionaceous [Cd2Br2] subunits. The 1-D hexagonal [CdCl2]n grid inorganic chains in 3 are generated by vertex-loss cubane-like [Cd3Cl4] motifs through sharing faces, which are further connected by L1 ligands to give a 2-D hybrid layer. For compound 4, the L2 ligands and 4-connected Cd centres link each other to give a 1-D single chain. In 5 and 6, [Cd2Br4] units are connected by L3 and L4 to generate a 2-D (4, 4) net and 1-D double chain structure, respectively. Four independent [CdI2] centres and four L4 ligands in 7 generate an extraordinarily large [Cd4N24C24] 52-membered cycle. The varying structures of 1–7 indicate that the spacer length of the bis(benzotriazole)alkane ligands and counter-anions play an essential role in the formation of the framework of the Cd(II) hybrid materials. Strong π–π stacking interactions between the benzotriazole ligands pack these low-dimensional hybrid chains or layers into high-dimensional supramolecular frameworks. The UV-vis diffuse reflectance spectra and solid state luminescence measurements show that compounds 1–7 are potential semiconductor and photoluminescence materials.

Ionothermal synthesis of a new (4,12)-connected heterometallic iodoplumbate with [Pb4(OH)4] cubane as joint points of the helices

The first ionothermal case of the heterometallic iodoplumbate, [CuPb2I2Br(OH)2] (1), was prepared using 1-ethyl-3-methyl imidazolium bromide as a solvent. It exhibits an unprecedented (4,12)-connected topology with [Pb4(OH)4] cubane as the joint points of the helices.

Effects of Additives on the Thermostability of Chloroperoxidase

The effects of several polyhydroxy compounds (glucose, fructose, gumsugar, galactose, trehalose, dextran, xylose, PEG200, glycerin) and surfactant (dioctyl sulfosuccinate sodium salt, AOT) on the catalytic activity and thermal stability of chloroperoxidase (CPO) in aqueous systems were investigated at various temperatures. A 25% superactivity was found in AOT solutions at 25 °C, and it could be maintained during the 882 h. PEG200 and glycerin were proven to be the most efficient stabilizer for CPO in temperatures ranging from 25 to 60 °C. Trehalose is more helpful than other sugars for extended storage of CPO. These results are promising in view of industrial applications of this versatile biological catalyst. The protective mechanism of various additives on CPO was discussed.

An unusual uninodal 10-connected self-penetrating network built from sixteen-nuclear hybrid cadmium clusters

The unusual 10-connected self-penetrating metal–organic framework based on sixteen-nuclear hybrid cadmium clusters has been constructed using 1,2,4-triazole, SCN− and F− as coligands, which represents the highest-connected uninodal network topology presently known for self-penetrating systems.

Channel partition into nanoscale polyhedral cages of a triple-self-interpenetrated metal-organic framework with high CO2 uptake.

Reported herein is a novel porous metal-organic framework (MOF) exhibiting unique nanoscale cages derived from the 3-fold self-interpenetration of chiral eta networks based on trifurcate {Zn2(CO2)3} building blocks and 1,3,5-tris(4-carboxyphenyl)benzene ligands. The attractive self-interpenetrated structural features contribute to the highest CO2 uptake capacity and CO2 binding ability among the interpenetrated MOFs.

An unusual (3,6)-connected microporous metal–organic framework based on tetrahedral Zn4 clusters with selective adsorption of CO2

A novel 3D microporous metal–organic framework based on tetrahedral Zn4 clusters has been synthesized and characterized, which presents an unprecedented (3,6)-connected (4·62)3(43·66·86) topology, and the capability of selective adsorption of CO2.

Crystalline 3D open-framework halogeno(cyano)cuprates synthesized in ionic liquids

Imidazolium-based ionic liquids are firstly utilized as the solvent, structure-directing agent, charge compensating agent, as well as reaction sources to give two novel crystalline 3D open-framework halogeno(cyano)cuprates showing strong luminescence.

Biocatalytic synthesis of C3 chiral building blocks by chloroperoxidase‐catalyzed enantioselective halo‐hydroxylation and epoxidation in the presence of ionic liquids

The optically active C3 synthetic blocks are remarkably versatile intermediates for the synthesis of numerous pharmaceuticals and agrochemicals. This work provides a simple and efficient enzymatic synthetic route for the environment‐friendly synthesis of C3 chiral building blocks. Chloroperoxidase (CPO)‐catalyzed enantioselective halo‐hydroxylation and epoxidation of chloropropene and allyl alcohol was employed to prepare C3 chiral building blocks in this work, including (R)‐2,3‐dichloro‐1‐propanol (DCP*), (R)‐2,3‐epoxy‐1‐propanol (GLD*), and (R)‐3‐chloro‐1‐2‐propanediol (CPD*). The ee values of the formed C3 chiral building blocks DCP*, CPD*, and glycidol were 98.1, 97.5, and 96.7%, respectively. Moreover, the use of small amount of imidazolium ionic liquid enhanced the yield efficiently due to the increase of solubility of hydrophobic organic substrates in aqueous reaction media, as well as the improvement of affinity and selectivity of CPO to substrate.

Hydrothermal synthesis, crystal structures, and blue photoluminescence of two 2-D Ag–1,2,4-triazolate coordination polymers with 4462 topology

Two 2-D metal-organic coordination polymers, {[Ag(NH2–BPT)] · NO3} n (1) and {[Ag(BPT)] · H2O} n (2), have been synthesized via self-assembly of AgNO3 and 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (NH2–BPT) under hydrothermal conditions by controlling the reaction temperatures. Lower reaction temperature (140°C) led to formation of 1, which crystallizes in the monoclinic system, space group C2/c, a = 24.001(3), b = 15.844(2), and c = 12.981(3) Å, V = 2996.8(6) Å3, Z = 8. When the temperature was increased to 180°C, in situ deaminization of the organic ligand led to crystallization of 2 (space group P21 /n, a = 7.3106(10), b = 19.633(2), and c = 9.0596(16) Å, V = 1190.2(3) Å3, Z = 4). The NH2–BPT in 1 and BPT in 2 are μ4 tetradentate utilizing two triazolyl and two pyridyl nitrogens, generating an unusual 2-D layer, in which binuclear Ag(I) motifs and organic ligands are four-connecting nodes that inter-link in 4462 topology. Adjacent 2-D metal-organic layers are linked by a system of hydrogen bonds to form 3-D supramolecular frameworks. Strong blue fluorescence emissions are observed for 1 and 2 in the solid state at ambient temperature.