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Two new different-bond-type hybrid compounds, (Hg6P4Cl3)(PbCl3) (1) and (Hg23P12)(ZnCl4)6 (2), with supramolecular interactions between host and guest moieties, which based on metal-pnicogen, pnicogen-pnicogen, and metal-halogen bonds were obtained by solid-state reactions. Compounds 1 and 2 show large second-harmonic-generation (SHG) activity and are transparent in the wide mid-IR region, providing an effective route for searching new IR nonlinear-optical material systems by combining two or more different bond types with no IR absorption within a single compound through supramolecular assembly. Theory predications based on first-principles calculations are also performed on the SHG properties of 1 and 2. [ABSTRACT FROM AUTHOR]

Chemiresistive sensing has been regarded as the key monitoring technique, while classic oxide gas detection devices always need an external power supply. In contrast, the bulk photovoltage of photoferroelectric materials could provide a controllable power source, holding a bright future in self-powered gas sensing. Herein, we present a new photoferroelectric ([ n -pentylaminium] 2 [ethylammonium] 2 Pb 3 I 10 , 1 ), which possesses large spontaneous polarization (∼4.8 μC/cm 2 ) and prominent visible-photoactive behaviors. Emphatically, driven by the bulk photovoltaic effect, 1 enables excellent self-powered sensing responses for NO 2 at room temperature, including extremely fast response/recovery speeds (0.15/0.16 min) and high sensitivity (0.03 ppm -1 ). Such figures of merit are superior to those of typical inorganic systems (e.g., ZnO) using an external power supply. Theoretical calculations and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements confirm the great selectivity of 1 for NO 2 . As far as we know, this is the first realization of ferroelectricity-driven self-powered gas detection. Our work sheds light on the self-powered sensing systems and provides a promising way to broaden the functionalities of photoferroelectrics.

Surface modification is a promising method to change the surface properties of nanomaterials, but it is limited in enhancing their intrinsic redox nature. In this work, a "filter amplifier" strategy is proposed for the first time to reverse the intrinsic redox nature of materials. This is demonstrated by coating a COF-316 layer with controlled thickness on TiO 2 to form core-sheath nanowire arrays. This unique structure forms a Z-scheme heterojunction to function as "a filter amplifier" which can conceal the intrinsic oxidative sites and increase the extrinsic reductive sites. Consequently, the selective response of TiO 2 is dramatically reversed from reductive ethanol and methanol to oxidative NO 2 . Moreover, TiO 2 @COF-316 provides remarkably improved sensitivity, response, and recovery speed, as well as unusual anti-humidity properties as compared with TiO 2 . This work not only provides a new strategy to rationally modulate the surface chemistry properties of nanomaterials but also opens an avenue to design high-performance electronic devices with a Z-scheme heterojunction.

On-board fuel cell technology requires proton conducting materials with high conductivity not only at intermediate temperatures for work but also at room temperature and even at subzero temperature for startup when exposed to the colder climate. To develop such materials is still challenging because many promising candidates for the proton transport on the basis of extended microstructures of water molecules suffer from significant damage by heat at temperatures above 80 °C or by freeze below -5 °C. Here we show imidazole loaded tetrahedral polyimides with mesopores and good stability (Im@Td-PNDI 1 and Im@Td-PPI 2) exhibiting a high anhydrous proton conductivity over a wide temperature range from -40 to 90 °C. Among all anhydrous proton conductors, the conductivity of 2 is the highest at temperatures below 40 °C and comparable with the best materials, His@[Al(OH)(1,4-ndc)]n and [Zn3(H2PO4)6(H2O)3](Hbim), above 40 °C.

Photochromism of N-methyl-4,4'-bipyridinium (MQ(+)) salts and their metal complexes has never been reported. A series of MQ(+) coordinated halozinc complexes [(MQ)ZnX(3)] (X = Cl (1), Br (2), I (3)) and [(MQ)ZnCl(1.53)I(1.47)](2)(MQ)ZnCl(1.68)I(1.32) (4), with better physicochemical stability than halide salts of the MQ(+) cation, have been found to exhibit different photochromic behaviors. Compounds 1-3 are isostructural, but only 1 and 2 show photochromism. Introduction of partial Cl atoms to nonphotochromic compound 3 yields compound 4, which also displays photochromism. The photochromic response of 1, 2, and 4 indicates the presence of their long-lived charge separation states, which originate from X → MQ(+) electron transfer according to ESR and XPS measurements. Studies on the influence of different coordinated halogen atoms demonstrate that the Cl atom may be a more suitable electron donor than Br and I atoms to design redox photochromic metal complexes.

A novel one-dimensional (1-D) mixed-valent thioarsenate (III, V), {[Mn(phen)](3)(As(V)S(4))(As(III)S(3))}(n)·nH(2)O (1), with a noncentrosymmetric (NCS) polar packing arrangement has been obtained under solvothermal conditions. The noncondensed (As(III)S(3))(3-) anion in 1 is stabilized by coordinating to [Mn(II)(phen)](2+) complex cations and exhibits an unprecedented μ(3)-1,2κS:2,3κS':3κS'' linkage mode. Compound 1 represents the first example of the stabilization of noncondensed (MQ(3))(3-) (M = As, Sb; Q = S, Se) species only in the coordination of TM(II) complex cations (TM = transition-metal) and the first observation of the coexistence of the (As(V)S(4))(3-) tetrahedron and the noncondensed (As(III)S(3))(3-) pyramid in a single compound. Of particular interest, compound 1 is also an antiferromagnet with T(N) = 31 K, and exhibits photoluminescence (PL) with a maximum emission at about 438 nm and a second harmonic generation (SHG) response., (© 2011 American Chemical Society)