Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

Fabrication of Superhydrophobic Cellulose-Based Materials through a Solution-Immersion Process

An industrial waterproof reagent [(potassium methyl siliconate) (PMS)] was used for fabricating a superhydrophobic surface on a cellulose-based material (cotton fabric or paper) through a solution-immersion method. This method involves a hydrogen bond assembly and a polycondensation process. The silanol, which was formed by a reaction of PMS aqueous solution with CO2, Was assembled on the cellulose molecule surface via hydrogen bond interactions. The polymethylsilsesquioxane coatings were prepared by a polycondensation reaction of the hydroxyl between cellulose and silatiol. The superhydrophobic cellulose materials were characterized by FTIR spectroscopy, thermogravimetry, and surface analysis (XPS, FESEM, AFM, and contact angle measurements).

Sulfonated poly(arylene-co-imide)s as water stable proton exchange membrane materials for fuel cells

A novel sulfonated poly(arylene-co-imide)s were synthesized by Ni(0) catalytic copolymerization of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and naphthalimide dichloride monomer. The synthesized copolymers with the - SO3H group on the side-chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. Because of the introduction of electron donating phenoxy groups into naphthalimide moieties, the hydrolysis of the imide rings was depressed. The resulting copolymers exhibited excellent water stability. The copolymer membranes display no apparently change in appearance, flexibility, and toughness after a soaking treatment in pressurized water at 140 degrees C for 250 h.

New organic-inorganic perovskite materials with different optical properties modulated by different inorganic sheets

New organic-inorganic perovskites with different PbBr perovskite sheets stabilized by 3- or 4-an-tidinopyridine were synthesized and structurally characterized. 4-Amidinopyridine constructs < 001 >-oriented perovskite with inorganic sheets made up of typical corner-sharing octahedra of PbBr2. Analogous chemistry in the presence of 3-amidinopyridine under the same conditions results in an unusual hybrid perovskite with the inorganic sheets showing a novel framework including both corner-sharing and edge-sharing PbBr2, which is different from any previously reported ones.

Synthesis and Characterization of Urea Bridged Hybrid Periodic Mesoporous Organosilica Materials

Urea bridged organic-inorganic hybrid mesoporous SiO2 materials (U-BSQMs) were synthesized through a sol-gel procedure by co-condensation of bis(triethoxysilyl propyl) urea (BSPU) under basic conditions using cetyltrimethylammonium bromide (CTAB) as organic template. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the mesoporous structure of the sample. Fourier-transform infrared spectroscopy (FT-IR), solid state CP-MAS NMR spectroscopy of Si-29 (Si-29, CP-MAS NMR) and C-13 (C-13 CP NMR) indicated that most of the Si-C bonds are unbroken during the synthesis process.

Silica Materials Doped with Bifunctional Ionic Liquid Extractant for Yttrium Extraction

Two new silica-based organic-inorganic hybrid materials (B104SGs and O104SGs) doped with a binary mixture of imidazolium and phosphonium ionic liquids have been synthesized and used as sorbents in batch system for rare earths (RE) separation. Imidazolium ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate (C(4)mim(+)PF(6)(-)) or 1-octyl-3-methylimidazolium hexafluorophosphate (C(8)mim(+)PF(6)(-)) acted as porogens to prepare porous materials and additives to stabilize extractant within silica gel.

Near-infrared luminescent mesoporous MCM-41 materials covalently bonded with ternary thulium complexes

Two beta-diketones 4,4,4-trifluoro-1-2-thenoyl-1,3-butanedione (Htta) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (Htfnb), which contain trifluoroalkyl chain, were selected as the main sensitizer for synthesizing Tm(L)(3)phen (L = tta, tfnb) complexes. The two near-infrared (NIR) luminescent thulium complexes have been covalently bonded to the ordered mesoporous material MCM-41 via a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) [The resultant mesoporous materials are denoted as Tm(L)(3)phen-MCM-41 (L = tta, tfnb)]. The Tm(L)(3)phen-MCM-41 (L = tta, tfnb) mesoporous materials were characterized by small-angle Xray diffraction (XRD) and N-2 adsorption/desorption, and they show characteristic mesoporous structure of MCM-41.

A study on the near-infrared luminescent properties of xerogel materials doped with dysprosium complexes

A series of dysprosium complex doped xerogels with the same first ligand (acac = acetylacetone) and different neutral ligands were synthesized in situ via a sol-gel process. The Fourier transform infrared (FTIR) spectra, diffuse reflectance (DR) spectra, and near-infrared (NIR) luminescent properties of dysprosium complexes and dysprosium complex doped xerogels are described in detail. The results reveal that the dysprosium complex is successfully synthesized in situ in the corresponding xerogel. Excitation at the maximum absorption wavelength of the ligands resulted in the characteristic NIR luminescence of the Dy3+ ion, which contributes to the energy transfer from the ligands to the central Dy3+ ion in both the dysprosium complexes and xerogels via an antenna effect.

Construction and Photoluminescence of Monophase Hybrid Materials Derived from a Urea-Based Bis-Silylated Bipyridine

A urea-based bis-silylated bipyridine ligand derived from 4,4'-diamino-2,2'-bipyridine has been prepared. Organic-inorganic hybrid materials with a high loading of lanthanide 2,2-bipyridine moieties were obtained by using the silylated bipyridine as the only siloxane network precursor in the presence of lanthanide ions (or lanthanide complexes). The in-situ formation of lanthanide complexes from lanthanide ions and the silylated bipyridine during the sol-gel processing was confirmed by the luminescence behavior of the obtained hybrid materials and that of the corresponding pure lanthanide complex [Ln(bpy)(2)Cl-3 center dot 2H(2)O].

Novel Near-Infrared Luminescent Hybrid Materials Covalently Linking with Lanthanide [Nd(III), Er(III), Yb(III), and Sm(III)] Complexes via a Primary beta-Diketone Ligand: Synthesis and Photophysical Studies

A series of novel, colorless, and transparent sot-gel derived hybrid materials Ln-DBM-Si covalently grafted with Ln(DBM-OH)(3)center dot 2H(2)O (where DBM-OH = o-hydroxydibenzoylmethane, Ln = Nd, Er, Yb, and Sin) were prepared through the primary beta-diketone ligand DBM-OH. The structures and optical properties of Ln-DBM-Si were studied in detail. The investigation results revealed that the lanthanide complexes were successfully in situ grafted into the corresponding hybrids Ln-DBM-Si. Upon excitation at the maximum absorption of ligands, the resultant materials displayed excellent near-infrared luminescence.

Near-infrared luminescent xerogel materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III)] complexes

A beta-diketone ligand 4,4,5,5,5-pentafluoro-1-(2-naphthyl)-1,3-butanedione (Hpfnp), which contains a pentafluoroalkyl chain, was synthesized as the main sensitizer for synthesizing new near-infrared (NIR) luminescent Ln(pfnp)(3)phen (phen = 1,10-phenanthroline) (Ln = Er, Nd, Yb, Sm) complexes. At the same time, a series of lanthanide complexes covalently bonded to xerogels by the ligand 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) were synthesized in situ via a sol-gel process. [The obtained materials are denoted as xerogel-bonded Ln complexes (Ln = Er, Nd, Yb, Sm).] The single crystal structures of the Ln(pfnp) 3phen complexes were determined.

Thiacalix[4]arene-Supported Planar Ln(4) (Ln = Tb-III, Dy-III) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H(4)TC4A.

Removal of Cr(III, VI) by quaternary ammonium and quaternary phosphonium ionic liquids functionalized silica materials

A series of silica-based organic–inorganic hybrid materials were prepared by the sol–gel process for Cr(III) and Cr(VI) adsorption. These silica materials generally had high surface areas, good physical–chemical stability and high thermal stability. Trialkylmethylammonium bis 2,4,4-trimethylpentylphosphinate ([A336][C272]) and trihexyl(tetradecyl)phosphonium bis 2,4,4-trimethylpentylphosphinate (Cyphos IL 104) were explored as porogens to prepare porous silica and as extractants to extract chromium ions. Cyphos IL 104 and [A336][C272] functionalized silica sorbents (SG-2, SG-5) can be effectively used for the removal of Cr(III) and Cr(VI) from aqueous solutions by adjusting pH values, whereas trialkylmethylammonium chloride (Aliquat 336) and bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272) functionalized silica sorbents (SG-3, SG-4) can only be used for the removal of the single chromium species, Cr(VI) or Cr(III).

Multiform oxide optical materials via the versatile Pechini-type sol-gel process: Synthesis and characteristics

This feature article highlights work from the authors' laboratories on the various kinds of oxide optical materials, mainly luminescence and pigment materials with different forms (powder, core-shell structures, thin film and patterning) prepared by the Pechini-type sol-gel (PSG) process. The PSG process, which uses the common metal salts (nitrates, acetates, chlorides, etc.) as precursors and citric acid (CA) as chelating ligands of metal ions and polyhydroxy alcohol (such as ethylene glycol or poly ethylene glycol) as a cross-linking agent to form a polymeric resin on molecular level, reduces segregation of particular metal ions and ensures compositional homogeneity. This process can overcome most of the difficulties and disadvantages that frequently occur in the alkoxides based sol-gel process.