Jinjun Ren

Inhomogeneous broadening, luminescence origin and optical amplification in bismuth-doped glass

Absorption and luminescence spectra and optical amplification in bismuth-doped germanate silicate glass were investigated. Two kinds of bismuth ion valence states could exist in the glass. One is Bi2+, which has shown red luminescence, another might be Bi+, which is the active center for infrared luminescence. The infrared luminescence excited at 700, 800, and 980 nm should be ascribed to the electronic transition 3P1 --> 3P0 of Bi+ ions in three distinct sites. The shifting, broadening, and multiple configuration of the luminescence could be due to the randomly disorder of local environment and multiple sites of the active centers. In this glass, obvious optical amplification was realized at 1300 nm wavelength when excited at 808 and 980 nm, respectively.

Preparation of Bifunctional Mesoporous Silica Nanoparticles by Orthogonal Click Reactions and Their Application in Cooperative Catalysis

The synthesis of bifunctional mesoporous silica nanoparticles is described. Two chemically orthogonal functionalities are incorporated into mesoporous silica by co-condensation of tetraethoxysilane with two orthogonally functionalized triethoxyalkylsilanes. Post-functionalization is achieved by orthogonal surface chemistry. A thiol-ene reaction, Cu-catalyzed 1,3-dipolar alkyne/azide cycloaddition, and a radical nitroxide exchange reaction are used as orthogonal processes to install two functionalities at the surface that differ in reactivity. Preparation of mesoporous silica nanoparticles bearing acidic and basic sites by this approach is discussed. Particles are analyzed by solid state NMR spectroscopy, elemental analysis, infrared-spectroscopy, and scanning electron microscopy. As a first application, these particles are successfully used as cooperative catalysts in the Henry reaction.

Frustrated Lewis pair modification by 1,1-carboboration: disclosure of a phosphine oxide triggered nitrogen monoxide addition to an intramolecular P/B frustrated Lewis pair.

The vicinal frustrated Lewis pair (FLP) mes2P-CH2CH2-B(C6F5)2 (3) reacts with phenyl(trimethylsilyl)acetylene by 1,1-carboboration to give the extended C3-bridged FLP 6 featuring a substituted vinylborane subunit. The FLP 6 actively cleaves dihydrogen. The FLP 3 also undergoes a 1,1-carboboration reaction with diphenylphosphino(trimethylsilyl)acetylene to give the P/B/P FLP 11 that features a central unsaturated four-membered heterocyclic P/B FLP and a pendant CH2CH2-Pmes2 functional group. Compound 11 reacts with nitric oxide (NO) by oxidation of the pendant Pmes2 unit to the P(O)mes2 phosphine oxide and N,N-addition of the P/B FLP unit to NO to yield the persistent P/B/PO FLPNO aminoxyl radical 14. This reaction is initiated by P(O)mes2 formation and opening of the central Ph2P···B(C6F5)2 linkage triggered by the pendant CH2CH2-P(O)mes2 group.

Enhanced broadband near-infrared luminescence in transparent silicate glass ceramics containing Yb3+ ions and Ni2+-doped LiGa5O8 nanocrystals

Spectral properties of Yb3+∕Ni2+ codoped transparent silicate glass ceramics containing LiGa5O8 nanocrystals were investigated. The near-infrared emission intensity of Ni2+ was largely increased with Yb3+ codoping due to Yb3+→Ni2+ energy transfer. The qualitative calculation of the energy transfer constant Cs-a and rate Ps-a showed that the Yb3+→Ni2+ energy transfer was much greater than in the opposite direction. Yb3+∕Ni2+ codoped glass ceramics with 0.75mol% Yb2O3 exhibited a near-infrared emission with full width at half maximum of 290nm and fluorescent lifetime of 920μs. The glass ceramics are promising for broadband optical amplification.

A Homonuclear Rotational Echo Double-Resonance Method for Measuring Site-Resolved Distance Distributions in I=1/2 Spin Pairs, Clusters, and Multispin Systems†

The unique power and potential of high-resolution solid-state NMR spectroscopy to provide structure information at the atomic level for complex, disordered, and molecular solids have been amply demonstrated. 2] In particular, the analysis of internuclear dipole–dipole couplings can provide information about distances, bond connectivities, and spatial spin distributions. For heteronuclear spin systems, one of the most powerful methods to accomplish this in a site-resolved fashion has been the rotational echo double-resonance (REDOR) technique, where a difference signal is measured of signal amplitudes S0 with the interaction absent (owing to magic-angle spinning, MAS) and reduced signal amplitudes S’ with the interaction recoupled (through application of inversion pulses during the rotor period). REDOR has been widely used for measuring internuclear distances and their distributions in biological systems and inorganic materials alike and has been adapted in many different versions and variants. In contrast, an analogous homonuclear difference strategy of similar versatility has up to now not yet been realized for multispin systems. Although a large variety of homonuclear recoupling approaches have been published, their calibration to yield information on dipolar couplings on the basis of simulations or model compound work has remained a difficult issue. While promising progress was recently reported using improved double-quantum excitation strategies, important remaining issues include the limited efficiency of double-quantum coherence excitation, T2 relaxation, and dipolar truncation effects. The only homonuclear difference method known so far involves an excitation of zero-quantum coherences using the “transverseecho simple excitation for the dephasing of rotational-echo amplitude (t-SEDRA)” method, where the dephasing of transverse magnetization Ix1 + Ix2 is compared with that under the influence of an effective Hamiltonian [Eq. (1)]. While transverse-echo SEDRA does succeed in eliminating the influence of T2 relaxation upon the experimental data, applications to systems beyond isolated two-spin pairs have not been reported so far.

Blue emission from Eu2+-doped high silica glass by near-infrared femtosecond laser irradiation

Eu2+-doped high silica glass (HSG) is fabricated by sintering porous glass which is impregnated with europium ions. Eu2+-doped HSG is revealed to yield intense blue emission excited by ultraviolet (UV) light and near-infrared femtosecond laser. The emission profile obtained by UV excitation can be well traced by near-infrared femtosecond laser. The upconversion emission excited by 800 nm femtosecond laser is considered to be related to a two-photon absorption process from the relationship between the integrated intensity and the pump power. A tentative scheme of upconverted blue emission from Eu2+-doped HSG was also proposed. The HSG materials presented herein are expected to find applications in high density optical storage and three-dimensional color displays.

Optical amplification near 1300 nm in bismuth-doped strontium germanate glass

We demonstrate the broadband optical amplification in bismuth-doped strontium germanate glass with 808 nm and 980 nm laser diodes (LDs) as excitation sources. The net optical gain has been obtained within the wavelength region of 1272 to 1348 nm with 808 nm laser diode under 0.97 W power. The maximum gain and gain coefficients are 1.23 and 1.03 cm−1 at 1315 nm, respectively. The signal increment at 1300 nm is 2.8 times with 980 nm LD, under 3 W power. The differential thermal analysis measurement reveals the good thermal stability of the studied glass. This glass could be suggested as a promising gain medium for broadband optical amplifiers.

P3Se4 (+): A Binary Phosphorus-Selenium Cation

Although a fairly large number of binary group 15/16 element cations have been reported, no example involving phosphorus in combination with a group 16 element has been synthesized and characterized to date. In this contribution is reported the synthesis and structural characterization of the first example of such a cation, namely a nortricyclane-type [P3Se4](+). This cation has been independently discovered by three groups through three different synthetic routes, as described herein. The molecular and electronic structure of the [P3Se4](+) cage and its crystal properties in the solid state have been characterized comprehensively by using X-ray diffraction, Raman, and nuclear magnetic resonance spectroscopies, as well as quantum chemical calculations.

Indirect “No-Bond” 31P···31P Spin–Spin Couplings in P,P-[3]Ferrocenophanes: Insights from Solid-State NMR Spectroscopy and DFT Calculations

No-bond (31)P-(31)P indirect dipolar couplings, which arise from the transmission of nuclear spin polarization through interaction of proximal nonbonded electron pairs have been investigated in the solid state for a series of closely related substituted P,P-[3]ferrocenophanes and model systems. Through variation and combination of ligands (phenyl, cyclohexyl, isopropyl) at the two phosphorus sites, the P···P distances in these compounds can be varied from 3.49 to 4.06 Å. Thus, the distance dependence of the indirect no-bond coupling constant J(nb) can be studied in a series of closely related compounds. One- and two-dimensional solid-state NMR experiments serve to establish the character of these couplings and to measure the isotropic coupling constants J(iso), which were found to range between 12 and 250 Hz. To develop an understanding of the magnitude of J(nb) in terms of molecular structure, their dependences on intramolecular internuclear distances and relative orbital orientations is discussed by DFT-calculations on suitable models. In agreement with the literature the dependence of J(nb) on the P···P distance is found to be exponential; however, the steepness of this curve is highly dependent on the internuclear equilibrium distance. For a quantitative description, the off-diagonal elements of the expectation value of the Kohn-Sham-Fock operator in the LMO basis for the LMOs of the two phosphorus lone-pairs is proposed. This parameter correlates linearly with the calculated J(nb) values and possesses the same distance-dependence. In addition, the simulations indicate a distinct dependence of J(nb) on the dihedral angle defined by the two C-P bonds providing ligation to the molecular backbone. For disordered materials or those featuring multiple sites, conformers, and/or polymorphism, a new double-quantum NMR method termed DQ-DRENAR can be used to conveniently measure internuclear (31)P-(31)P distances. If conducted on compounds with known P···P distances, such measurements can also serve to estimate the magnitude of the anisotropy ΔJ of these no-bond indirect spin-spin couplings. The DFT results suggest that in the present series of compounds the magnitude of ΔJ is strongly correlated with that of the isotropic component, as both parameters have analogous distance dependences. While our studies indicate a sizable J-anisotropy for the model compound 1,8-bis(diphenylphosphino)napthalene (ΔJ ~ -70 Hz), the corresponding values for the P,P-[3]ferrocenophanes are significantly smaller, affecting their DQ-DRENAR curves only in a minor way. Based on the above insights, the structural aspects of conformational disorder and polymorphism observed in some of the P,P-[3]ferrocenophanes are discussed.

Ultrabroadband Infrared Luminescence and Optical Amplification in Bismuth-Doped Germanosilicate Glass

This letter reports the ultrabroadband infrared luminescence from 1000- to 1700-nm wavelength range and demonstrate optical amplification at the second optical communication window in a novel bismuth-doped germanosilicate glass. The full-width at half-maximum of the luminescence is about 300 nm and the optical gain is larger than 1.37 within the wavelength region from 1272 to 1348 nm with pump power 0.97 W. This material could be useful to fabricate ultrabroadband optical fiber amplifiers.