Inorganic–Organic Heteropolyacid–Gold(I) Hybrids: Structures and Catalytic Applications

Gold(I)‐polyoxometalate hybrid complexes 1 – 4 ([PPh₃AuMeCN]_xH_4?xSiW₁₂O₄₀, x=1–4) were synthesized and characterized. The structure of the primary gold(I)–polyoxometalate 1 (x=1) was fully ascertained by XRD, FTIR, ³¹P and ²⁹Si magic‐angle spinning (MAS) NMR, mass spectroscopy, and SEM–energy dispersive X‐ray spectroscopy (EDX) techniques. Moreover, this complex exhibited better catalytic activity and selectivity compared with standard, homogeneous, gold catalysts in the new rearrangement of propargylic gem‐diesters.     

Inorganic–Organic Hybrid Polyoxoniobates: Polyoxoniobate Metal Complex Cage and Cage Framework

The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K₄@{[Cu₂₉(OH)₇(H₂O)₂(en)₈(trz)₂₁][Nb₂₄O₆₇(OH)₂(H₂O)₃]₄} and [Cu(en)₂]@{[Cu₂(en)₂(trz)₂]₆(Nb₆₈O₁₈₈)} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic–organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage‐based extended assembly to form a 3D cage framework {[Cu(en)₂]@{[Cu₂(trz)₂(en)₂]₆[H₁₀Nb₆₈O₁₈₈]}}. These materials exhibit visible‐light‐driven photocatalytic H₂ evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic–organic hybrid PONb chemistry.     

CuSbS2‐Sensitized Inorganic–Organic Heterojunction Solar Cells Fabricated Using a Metal–Thiourea Complex Solution

The device performance of sensitizer‐architecture solar cells based on a CuSbS₂ light sensitizer is presented. The device consists of F‐doped SnO₂ substrate/TiO₂ blocking layer/mesoporous TiO₂/CuSbS₂/hole‐transporting material/Au electrode. The CuSbS₂ was deposited by repeated cycles of spin coating of a Cu‐Sb‐thiourea complex solution and thermal decomposition, followed by annealing in Ar at 500 °C. Poly(2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7(2,1,3‐benzothiadiazole)) (PCPDTBT) was used as the hole‐transporting material. The best‐performing cell exhibited a 3.1 % device efficiency, with a short‐circuit current density of 21.5 mA cm^?2, an open‐circuit voltage of 304 mV, and a fill factor of 46.8 %.     

Inorganic–Organic Hybrid Nanoparticles with Biocompatible Calcium Phosphate Thin Shells for Fluorescence Enhancement

Polymeric micelles consisting of asymmetric triblock copolymers were successfully used for fabrication of robust hybrid nanoparticles with highly biocompatible calcium phosphate shells. The hydrophobic polystyrene core encapsulates hydrophobic fluorescent dyes such as Nile red. The anionic polyacrylic acid provides the site for the mineralization reaction of calcium phosphate. The polyethylene glycol corona stabilizes the hybrid nanoparticles. Fluorescent dyes can be used as imaging agents for determining the location of the nanoparticles and to give an observable indication of drug delivery, while the calcium phosphate shell can enhance the fluorescence of the encapsulated dye.     

Dendronized polymers via Diels–Alder “click” reaction

A modular approach toward the synthesis of polymers containing dendron groups as side chains is developed using the Diels–Alder “click” reaction. For this purpose, a styrene‐based polymer appended with anthracene groups as reactive side chains was synthesized. First through third‐generation polyester dendrons containing furan‐protected maleimide groups at their focal point were synthesized. Facile, reagent‐free, thermal Diels–Alder cycloaddition between the anthracene‐containing polymer and latent‐reactive dendrons leads to quantitative functionalization of the polymer chains to afford dendronized polymers. The efficiency of this functionalization step was monitored using ¹H and ¹³C NMR spectroscopy and FTIR and UV–vis spectrometry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 410–416, 2010     

Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.