Wei-Wei Xiong

Growing Crystalline Chalcogenidoarsenates in Surfactants: From Zero-Dimensional Cluster to Three-Dimensional Framework

Although surfactants have been widely used to tailor the size, shape, and surface properties of nanocrystals and control the pore size and phases of mesoporous frameworks, the use of surfactants as reaction media to grow chalcogenide crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These features suggest that surfactants could be promising reaction platforms for the development of novel chalcogenide crystals. In this work, we used chalcogenidoarsenates as a model system to demonstrate our strategy. By using three different surfactants as reaction media, we obtained a series of novel thioarsenates ranging from a zero-dimensional (0D) cluster to a three-dimensional (3D) framework, namely, [NH(4)](8)[Mn(2)As(4)S(16)] (1), [Mn(NH(3))(6)][Mn(2)As(2)S(8)(N(2)H(4))(2)] (2), [enH][Cu(3)As(2)S(5)] (3), and [NH(4)][MnAs(3)S(6)] (4). The band gaps (estimated from the steep absorption edges) were found to be 2.31 eV for 1 (0D), 2.46 eV for 2 (1D), 1.91 eV for 3 (2D), and 2.08 eV for 4 (3D). The magnetic study of 4 indicated weak antiferromagnetic behavior. Our strategy of growing crystalline materials in surfactants could offer exciting opportunities for preparing novel crystalline materials with diverse structures and interesting properties.

Surfactant media to grow new crystalline cobalt 1,3,5-benzenetricarboxylate metal-organic frameworks.

In this report, three new metal-organic frameworks (MOFs), [Co3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA)3·H2O (NTU-Z30), [Co(BTC)]·HTEA·H2O (NTU-Z31), [Co3(BTC)4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine, and NTU = Nanyang Technological University, have been successfully synthesized under surfactant media and have been carefully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and IR spectromtry. NTU-Z30 has an unusual trimeric [Co3(μ3-OH)(COO)7] secondary building unit (SBU), which is different from the well-known trimeric [Co3O(COO)6] SBU. The topology studies indicate that NTU-Z30 and NTU-Z32 possess two new topologies, 3,3,6,7-c net and 2,8-c net, respectively, while NTU-Z31 has a known topology rtl type (3,6-c net). Magnetic analyses show that all three materials have weak antiferromagnetic behavior. Furthermore, NTU-Z30 has been selected as the heterogeneous catalyst for the aerobic epoxidation of alkene, and our results show that this material exhibits excellent catalytic activity as well as good stability. Our success in growing new crystalline cobalt 1,3,5-benzenetricarboxylate MOFs under surfactant media could pave a new road to preparing new diverse crystalline inorganic materials through a surfactant-thermal method.

Surfactants as Promising Media for the Preparation of Crystalline Inorganic Materials

Given that surfactants can control the shape and size of micro-/nanoparticles, they should be able to direct the growth of bulk crystals. This Minireview summarizes recent developments in the application of surfactants for the preparation of new crystalline inorganic materials, including chalcogenides, metal-organic frameworks, and zeolite analogues. The roles of surfactants in different reaction systems are discussed.

New strategies to prepare crystalline chalcogenides

Because the structures and properties of crystalline metal chalcogenides are strongly dependent on their synthetic conditions, developing new methods to approach novel chalcogenides is highly desirable. This review will summarize the recent progress in growing crystalline chalcogenides through four new strategies: ionothermal, surfactant-thermal, hydrazine-thermal, and metal Zintl phase usage.

Largest discrete supertetrahedral clusters synthesized in ionic liquids

Four discrete T5 cluster compounds with Cu–M–S constituents (M = In for compound 1, Ga for 2–4) have been synthesized in an ionic liquid (IL) [Bmmim]Cl (Bmmim = 1-butyl-2,3-dimethyl-imidazolium), which represent the largest molecular clusters in a Tn series. The in situ decomposition of the IL generates the Bim ligand (Bim = 1-butyl-2-methyl-imidazole) that directly coordinates to some of the corner Ga3+ ions of the T5 clusters in 3–4, leading to the formation of the first inorganic–organic hybrid T5 clusters. 2–4 show significantly broad photoluminescent emission bands ranging from 500 to 800 nm with a full width at half maximum (fwhm) at about 180 nm. This research provides a new method for synthesizing molecular metal chalcogenides that uses ILs as a reactive solvent and stabilizer.

Surfactant–Thermal Method to Synthesize a Novel Two‐Dimensional Oxochalcogenide

A new two-dimensional (2D) oxosulfide, (N2H4)2Mn3Sb4S8(μ3-OH)2 (1), has been successfully synthesized under surfactant-thermal conditions with hexadecyltributylphosphonium bromide as the surfactant. Compound 1 has a layered structure and contains a novel [Mn3(μ3-OH)2]n chain along the b-axis. The photocatalytic activity for compound 1 has been demonstrated under visible-light irradiation and continuous H2 evolution was observed. Our results indicate that surfactant-thermal synthesis could be a promising method for growing novel crystalline oxochalcogenides with interesting structures and properties.

[4 + 2] cycloaddition reaction to approach diazatwistpentacenes: synthesis, structures, physical properties, and self-assembly.

Three novel diazatwistpentacenes (1,4,6,13-tetraphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (1, IUPAC name: 9,11,14,16-tetraphenyl-1,6-dihydrobenzo[8,9]triphenyleno[2,3-g]phthalazine); 1,4-di(pyridin-2-yl)-6,13-diphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (2, IUPAC name: 9,16-diphenyl-11,14-di(pyridin-2-yl)-1,6-dihydrobenzo[8,9]triphenyleno[2,3-g]phthalazine); and 1,4-di(thien-2-yl)-6,13-diphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (3, IUPAC name: 9,16-diphenyl-11,14-di(thien-2-yl)-1,6-dihydrobenzo[8,9]triphenyleno[2,3-g]phthalazine)) have been successfully synthesized through [4 + 2] cycloaddition reaction involving in situ arynes as dienophiles and substituted 1,2,4,5-tetrazines as dienes. Their structures have been determined by single-crystal X-ray diffraction, confirming that all compounds have twisted configurations with torsion angles between the pyrene unit and the 2,3-diazaanthrance part as high as 21.52° (for 1), 24.74° (for 2), and 21.14° (for 3). The optical bandgaps for all compounds corroborate the values derived from CV. The calculation done by DFT shows that the HOMO-LUMO bandgaps are in good agreement with experimental data. Interestingly, the substituted groups (phenyl, pyridyl, thienyl) in the 1,4-positions did affect their self-assembly and the optical properties of as-resulted nanostructures. Under the same conditions, compounds 1-3 could self-assemble into different morphologies such as microrods (for 1), nanoprisms (for 2), and nanobelts (for 3). Moreover, the UV-vis absorption and emission spectra of as-prepared nanostructures were largely red-shifted, indicating J-type aggregation for all materials. Surprisingly, both 1 and 2 showed aggregation-induced emission (AIE) effect, while compound 3 showed aggregation-caused quenching (ACQ) effect. Our method to approach novel twisted azaacenes through [4 + 2] reaction could offer a new tool to develop unusual twisted conjugated materials for future optoelectronic applications.

1,5,9-Triaza-2,6,10-triphenylboracoronene: BN-Embedded Analogue of Coronene

A novel BN-fused coronene derivative 1,5,9-triaza-2,6,10-triphenylboracoronene (1) has been successfully synthesized in one step from 2,3,6,7,9,10-hexamethoxy-1,5,9-triamino-triphenylene. Compound 1 has been investigated using photophysical, electrochemical, and molecular simulation methods. Interestingly, three phenyl groups at B centers in compound 1 can be replaced by hydroxyl units stepwise through hydroxylation in wet organic solvents, leading to changes in the packing and physical properties.

Threading chalcogenide layers with polymer chains.

Inserting polymers into a crystalline inorganic matrix to understand the structure, position, and the structure-property relationships of the resulting composites is important for designing new inorganic-organic materials and tuning their properties. Single crystals of polymer-chalcogenide composites were successfully prepared by trapping polyethyleneglycol within a selenidostannate matrix under surfactant-thermal conditions. This work might provide a new strategy for preparing novel crystalline polymer-inorganic composites through encapsulating polymer chains within inorganic matrices.

A series of novel organically templated germanium antimony sulfides.

A series of novel organically templated germanium antimony sulfides have been solvothermally synthesized and structurally, thermally, and optically characterized. The compound [Me(2)NH(2)](6)[(Ge(2)Sb(2)S(7))(Ge(4)S(10))] (1) features two distinct tetranuclear [Ge(2)Sb(2)S(7)](2-) and [Ge(4)S(10)](4-) isolated clusters. The compound [(Me)(2)NH(2)][DabcoH](2)[Ge(2)Sb(3)S(10)] (2) (Dabco = triethylenediamine) features a 1D-[Ge(2)Sb(3)S(10)](n)(3n-) ribbon constructed with two [GeSbS(5)](n)(3n-) chains bridged by Sb(3+) ion in psi-SbS(4) configuration. Compounds [M(en)(3)][GeSb(2)S(6)] (M = Ni (3), Co (4) en = ethylenediamine) feature the unique 2D grid layer structures of [GeSb(2)S(6)](n)(2n-). The compound [(Me)(2)NH(2)](2)[GeSb(2)S(6)] (5) previously reported by us features a 3D chiral microporous structure with the chiral channels. The optical absorption spectra indicate that all the compounds are wide bandgap semiconductors. Thermal stabilities of these compounds have been investigated by thermogravimetric analyses (TGA).