Sheng-Ping Guo

A direct white-light-emitting metal-organic framework with tunable yellow-to-white photoluminescence by variation of excitation light.

A direct white-light metal-organic framework (MOF), [AgL](n) x nH(2)O (1, L = 4-cyanobenzoate), obtained by the reaction of deprotonated 4-cyanobenzoic acid and AgNO(3) in water, was found to exhibit tunable yellow-to-white photoluminescence by variation of excitation light. Interestingly, the close pure white emission of 1 has CIE-1931 chromaticity coordinates of (0.33, 0.34) when excited by 349-nm UV light, which is compatible to the light output of the deep UV LED.

A Series of New Infrared NLO Semiconductors, ZnY6Si2S14, AlxDy3(SiyAl1−y)S7, and Al0.33Sm3SiS7

Four new quaternary isostructural rare-earth thiosilicates, ZnY(6)Si(2)S(14) (1), Al(0.50)Dy(3)(Si(0.50)Al(0.50))S(7) (2), Al(0.38)Dy(3)(Si(0.85)Al(0.15))S(7) (3), and Al(0.33)Sm(3)SiS(7) (4), crystallized in the chiral and polar space group P6(3), have been prepared by a facile synthetic routine. Compounds 1-3 show strong second harmonic generation effects at 2.1 um with the intensities of 1, 2, and 3 being about 2, 2, and 1 times that of KTP (KTiOPO(4)), respectively. The calculated band structure of 1 implies that the optical absorptions of BLn(6)M(2)Q(14) and ALn(3)MQ(7) family compounds are mainly ascribed to the charge transitions from Q-p to Ln-4f (4d for Y) states. Compounds 2-4 exhibit antiferromagnetic-like interactions.

Electron‐Transfer Photochromism To Switch Bulk Second‐Order Nonlinear Optical Properties with High Contrast

The first bulk electron-transfer photochromic compound with intrinsic second-order nonlinear optical (NLO) photoswitching properties has been synthesized. This system employs an electron-transfer photoactive asymmetric viologen ligand coordinated to a zinc(II) center.

Stabilization of (SnS4)4− anion by coordinating to [TM(π-conjugated-ligand)m]n+ complex: a chain-like thiostannate(IV) {[Mn(phen)]2(SnS4)}n·nH2O exhibiting an unprecedented link mode of the (SnS4)4− anion

The stabilization of the (SnS4)4− anion in the coordination of [Mn(phen)]2+ complexes brings about a novel compound {[Mn(phen)]2(SnS4)}n·nH2O (1), in which an unprecedented link mode of the (SnS4)4− anion is observed. Theoretical calculations indicate that TM complexes with big π-conjugated ligands, such as [Mn(phen)]2+, can serve as an excellent electron reservoir to stabilize the (SnS4)4− anion in 1, despite its strong condensation tendency. Magnetic measurements show the presence of strong antiferromagnetic interactions between the Mn2+ ions in 1.

Large Crystal Growth and New Crystal Exploration of Mid-Infrared Second-Order Nonlinear Optical Materials

Mid-IR second-order NLO crystal is indispensable in the frequency conversion applications in the mid-IR region. Compared with DUV and UV/Vis/near-IR NLO crystals, practical mid-IR NLO crystals are relatively rare, and many of them are still at the stage of laboratory research. This chapter reviews the recent progress on the mid-IR NLO crystals, which mainly includes growing the classical mid-IR NLO crystals into large high-quality ones or into quasi-phase-matching structures that are suitable for the laser devices by various growth methods and exploring new potential mid-IR NLO crystals by introducing new design and synthesis strategies. Recent mid-IR NLO crystals can be divided into four categories, i.e., classical binary and ternary metal pnictides and chalcogenides, quaternary metal chalcogenides, binary and ternary metal halides, and different-bond-type hybrid compounds that contain at least two types of obviously different chemical bonds in the crystal structures. Metal pnictides and chalcogenides have got much attention on growing large crystals. Different-bond-type hybrid is a new family of mid-IR NLO materials, and many of them were found in the last decade. In metal halide system, both progress in growing large crystals and discovering new ones have been made.

Fe3S4 Nanoparticles Wrapped in an rGO Matrix for Promising Energy Storage: Outstanding Cyclic and Rate Performance

Iron sulfides/oxides/fluorides have been profoundly investigated as electrodes for rechargeable batteries recently in view of their high-theory capacities, low cost, and environmentally benign nature. Here, Fe3S4 nanoparticles (NPs) wrapped in reduced graphene oxide (Fe3S4 NPs@rGO) have been obtained using a simple one-pot hydrothermal approach, which is characterized using various techniques. As the anode for Li-ion batteries, Fe3S4 NPs@rGO displays a reversible discharge capacity of 950 mA h/g after 100 cycles at 0.1 A/g, and 720 mA h/g capacity can be achieved after 800 cycles even at 1 A/g. Even at 10 A/g, 462 mA h/g capacity can be maintained. The excellent electrochemical properties for Fe3S4 NPs@rGO can be ascribed to a collaborative effect between Fe3S4 NPs and an rGO matrix, which possess high Li-ion storage ability and excellent conductivity, respectively.

A series of pentanary inorganic supramolecular sulfides (A3X)[MB12(MS4)3] (A = K, Cs; X = Cl, Br, I; M = Ga, In, Gd) featuring B12S12 clusters

A series of new pentanary inorganic supramolecular sulfides (A3X)[MB12(MS4)3] (A = K, Cs; X = Cl, Br, I; M = Ga, In, Gd) have been synthesized using high-temperature solid-state reactions. They crystallize in the noncentrosymmetric hexagonal space group P6322. Their structures feature a MS4 tetrahedra saturated B12 icosahedron, and the latter is also alternately connected with a MS6 octahedron via face sharing to form a chain. [(A3X)2+]n polycationic chains fill in the 1D channels of the 3D open-framework {[MB12(MS4)3]2−}n. A discussion about their structural chemistry is also presented. Their second-order nonlinear optical (NLO) properties are calculated using Material Studio software, and the results show that this series of thioborates show tunable NLO properties.

Adduct-Type IR Nonlinear-Optical Crystal SbI 3 ·(S 8 ) 3 with a Large Second-Harmonic Generation and a High Laser-Induced DamageThreshold

A noncentrosymmetric adduct, SbI3·(S8)3, is obtained by a facile solution method. It crystallizes in the trigonal space group R3 m, and its structure features van der Waals force connected, isolated trigonal-pyramidal SbI3 and chairlike S8 units. SbI3·(S8)3 exhibits strong second-harmonic-generation responses around 4 times that of KH2PO4 (1.064 μm) and 1 times that of AgGaS2 (AGS; 2.1 μm) at 210-250 μm, respectively. Under both laser-radiation wavelengths, it exhibits type I phase-matching behavior. Its laser-induced damage threshold is measured to be around 26 times that of AGS under 1.064 μm. To better understand these optical data, theoretical calculations are performed to address its electronic structure and optical properties.

Crystal Chemistry and Photocatalytic Properties of RE4S4Te3 (RE = Gd, Ho, Er, Tm): Experimental and Theoretical Investigations

Reported are the synthesis and structural characterization of a new series of ternary rare-earth mix-chalcogenides RE4S4Te3 (RE = Gd, Ho, Er, Tm) that have been obtained from high-temperature solid state reactions. These compounds crystallize in Ho4S4Te2.68 structure types with monoclinic C2/ m and/or orthorhombic Immm space groups. The space group variation within this series is due to the position disorder along the Te plane (Te to TeA and TeB). The structural relationship and change between these two space groups are analyzed. It is realized that these compounds are all photocatalytic active under simulated sunlight. The trend of their photocatalytic activities and photocurrent responses is well-explained by using theoretical calculation as well as dipole moment analysis.

Synthesis, crystal and band structures, and optical properties of a new mixed-framework mercury selenide diselenite, (Hg3Se2)(Se2O5)†‡§

A new mixed-framework mercury selenide diselenite, (Hg(3)Se(2))(Se(2)O(5)) (1), has been prepared by a solid-state reaction and structurally characterized by single-crystal X-ray diffraction analysis. The crystal structure of 1 consists of parallel stair-like cationic (Hg(3)Se(2))(2+) chains, which are bridged by (Se(2)O(5))(2-) anionic groups to form a novel 2-D layered mixed-framework. The optical properties were investigated in terms of the diffuse reflectance and microscopic infrared spectra. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 is a semiconductor, and that the optical absorption of 1 is mainly ascribed to the charge transitions from the O-2p and Se(-II)-4p states to the Se(IV)-4p and Hg-6s states.