Jin-Shun Huang

A novel metal-organic network with high thermal stability: Nonlinear optical and photoluminescent properties

A novel zinc(II) 4-(5H-tetrazol)benzoic coordination polymer with an in situ generated tetrazole ligand exhibits the gsi (gamma-silicon) topology and high thermal stability; this compound possesses second-order nonlinear optical and interesting heat-induced photoluminescent properties.

A novel left-handed double helicate constructed from l-tartrate bridged molybdenum(vi) and gadolinium(iii) atomsElectronic supplementary information (ESI) available: crystallographic data, TGA, powder X-ray patterns, ORTEP structure and molar susceptibility plot for compound 1. See http://www.rsc.org/suppdata/cc/b3/b301542d/

The one-dimensional double helicate, [NH4][Mo2O4Gd(H2O)6(L-C4H2O6)2] x 4H2O (1), which was synthesized by the reaction of GdCl3, L-tartaric acid and ammonium molybdate in acidified water solution, is built up by two heft-handed single-helical chains, linked up further by eight-coordinated GdIII pieces in an enantiopure left-handed double helical configuration, of which each helix is formed by L-tartrate bridged six-coordinated MoVI atoms.

Inorganic Supramolecular Compounds with 3-D Chiral Frameworks Show Potential as Both Mid-IR Second-Order Nonlinear Optical and Piezoelectric Materials

Two inorganic supramolecular compounds, (Hg(6)P(3))(In(2)Cl(9)) (1) and (Hg(8)As(4))(Bi(3)Cl(13)) (2), which have chiral 3-D host frameworks with guest moieties filling the helical tunnels, have been synthesized. They both have large second-harmonic generation efficiencies, and compound 2 also exhibits obvious single-crystal piezoelectric performance. Theoretical studies from first-principles calculations were performed on their nonlinear optical (NLO) and piezoelectric properties, and results indicate that good NLO and piezoelectric materials can be obtained by designing both complicated polycations and polyanions with large molecular polarizability as functional components rather than traditional single polyanions.

Nonlinear optical and ferroelectric properties of a 3-D Cd(II) triazolate complex with a novel (63)2(610·85) topology

A novel 3-D (3,6)-connected topological architecture, obtained by reacting Cd(ClO4)2 x 6H2O with Htrtr (Htrtr = 3-(1,2,4-triazole-4-yl)-1H-1,2,4-triazole) under solvothermal conditions, presents a non-centrosymmetric polar packing arrangement, resulting in a strong second harmonic generation (SHG) response and ferroelectric property.

Eu3+-doped Tb3+ metal–organic frameworks emitting tunable three primary colors towards white light

A new bifunctional tetrazolate-5-carboxylate ligand has been prepared and employed in assembling 2-D Eu(III)–Zn(II) and Tb(III)–Zn(II) isostructural heterometallic MOFs with a (3,6)-connected kgd topology. The ligand in Tb3+ MOFs not only shows an antenna effect to transfer absorbed energy to Tb3+ centers to emit characteristic luminescence but also maintains good blue luminescent properties. Further, we have realized a rational design strategy to construct a series of Eu3+-doped Tb3+ MOFs emitting tunable three primary colors (RGB: red–green–blue) towards white light with high color rendering index and favorable correlated color temperature.

A ferroelectric inorganic–organic hybrid based on NLO-phore stilbazolium

A ferroelectric inorganic–organic hybrid based on in situ substituted stilbazolium cation (TAMS2+ = trimethylamino-N-methyl stilbazolium) has been obtained. Single-crystal X-ray structure analysis demonstrates that the NLO-phore organic component of the complex is embedded into the inorganic polymeric [Bi2Cl8]2− framework and shows a polar arrangement with the cooperation of the nonsymmetric inorganic component. The measurement of ferroelectric and nonlinear optical properties show typical ferroelectricity and second harmonic generation (SHG) responses as well as a significant improvement of the laser damage threshold and thermal stability of relative organic material.

Novel 3-D PtS-like tetrazolate-bridged manganese(II) complex exhibiting spin-canted antiferromagnetism and field-induced spin-flop transition

Two novel manganese(II) tetrazolate coordination polymers, Mn 3(Hbta) 4(mu 2 -OH) 2(H 2O).2H 2O ( 1) and Mn(bta)(H 2O) ( 2), were obtained by the hydrothermal reaction of MnCl 2.4H 2O with N, N-bis[1(2) H-tetrazol-5-yl]amine (H 2bta) in different pH values. Compound 1 exhibits a 2-D (4,4) layer structure, which is built from binuclear Mn 2(mu 2-OH) 2 subunits and mu 3-bridging Hbta (-) linkers. Compound 2 is a helical framework, and its 3-D PtS-like net is constructed by Mn 2(bta) 2 dimers and mu 5-bridging bta (2-) linkers. Magnetic measurements reveal that compound 1 displays an antiferromagnetic ordering, while compound 2 exhibits the coexistence of a spin-canted antiferromagnetic coupling and a field-induced spin-flop transition.

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.

Hydrothermal syntheses, crystal structures and luminescent properties of zinc(II) coordination polymers constructed by bifunctional tetrazolate-5-carboxylate ligands

Two bifunctional 1H-tetrazolate-5-carboxylate ligands with different flexibilities, H2tza (1H-tetrazolate-5-acetic acid) and H2tzf (1H-tetrazolate-5-formic acid), were employed in the construction of zinc(II) complexes in the presence/absence of secondary ligands such as 2,2′-bipy and 4,4′-bipy. Three tza coordination polymers and two tzf dinuclear complexes, namely [Zn(tza)(H2O)]n (1), [Zn3(tza)2Cl2(2,2′-bipy)2(H2O)2]n (2), [Zn2(tza)2(4,4′-bipy)]n (3), [Zn(tzf)(H2O)3]2·2H2O (4) and [Zn(tzf)(2,2′-bipy)(H2O)]2·H2O (5), were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Polymer 1 is a 3-D two-fold interpenetrating diamond-like network with tetranuclear [Zn(COO)]4 clusters as tertiary building units (TBUs) and µ3-κN3:κO2:κO1,N1 bridging tza as linkers. Polymer 2 presents a 2-D structure formed by the linkage of 1-D Zn-carboxylate [Zn(COO)]n helical chains and µ3-κN4:κO2:κO1,N1 bridging tza. In 3, 2-D (4,4) nets are built up with dinuclear [Zn(COO)]2 clusters and µ3-κN4:κO2:κO1,N1 bridging tza, which are pillared through 4,4′-bipy to gain a 3-D self-penetrating LB-1 (446108) topology. In dinuclear complexes 4 and 5, two Zn(II) atoms are bridged by a tzf ligand in a µ2-κN2:κO1,N1 fashion. The results denote that tetrazolate-5-carboxylate ligands can adopt variable coordination modes in the formation of the complexes, and different Zn-carboxylate aggregates can serve as tertiary building units (TBUs). The effects of the nature of tetrazolate-5-carboxylate ligands and secondary ligands, and hydrothermal reaction conditions on the structural topologies of the obtained complexes have been investigated. The photoluminescent properties and thermal stabilities of 1–5 have also been discussed.

Homochiral Zinc(II) Coordination Compounds Based on In-Situ-Generated Chiral Amino Acid–Tetrazole Ligands: Circular Dichroism, Excitation Light-Induced Tunable Photoluminescence, and Energetic Performance

We employed two pairs of new in-situ-generated chiral amino acid-tetrazole ligands in constructing homochiral Zn(II) coordination compounds: [Zn(tzet)]n (1a for (S)-tzet and 1b for (R)-tzet, H2tzet = N-[2-(1H-tetrazol-5-yl)ethyl]tryptophan) and [Zn(tzep)(H2O)2]·H2O (2a for (S)-tzep and 2b for (R)-tzep, H2tzep = N-[2-(1H-tetrazol-5-yl)ethyl]proline), which were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that 1 features a 2D homochiral framework generated by both tetrazolate and carboxylate bridges in tzet(2-) ligands. The isolated structure of 2 is stabilized by extensive hydrogen bonds, which leads to formation of a supramolecular 2D architecture. The absolute configuration induced at the nitrogen atoms of 1 and 2 is strictly related to the neighboring chiral carbon atoms by hydrogen-bond interactions. To further investigate their chirality, the combined experimental and theoretical analyses of circular dichroism spectra reveal the absolute configurations and nature of the Cotton effects. Solid-state excitation and emission spectra for 1 and 2 at room temperature were investigated with relevant density of states calculation, and tunable photoluminescence emission of 1 under different excitation wavelengths was discussed. As nitrogen-rich tetrazolate compounds, 1 and 2 possess higher enthalpies of combustion and may serve as a new family of promising energetic materials.