A basket tetradecavanadate cluster with blue luminescence

A blue luminescent tetradecavanadate compound, [Et4N]5[V14O36Cl], has been synthesized. It possesses an unprecedented half-open basket framework. Through the {ABAB}-type stacking, the {V14O36} clusters form infinite one-dimensional channels with considerable accessible volume in the crystalline state.     

New insights into the effects of self-association of the cation [Au[C(NHMe)(2)](2)](+) on its solid state structure and luminescence

Colorless [Au[C(NHMe)(2)](2)]X.H(2)O (X = Cl or Br) crystallize as dimers with Au.Au separations of 3.1231(3) A (Cl salt) and 3.1297(4) A (Br salt) between the linear, two-coordinate cations, and there is no direct interaction of Au(I) with the halide ions which are hydrogen bonded to ligand N-H groups and the water molecules. The luminescence of these dimers occurs at higher energy than that observed in extended chains of the same cation in the corresponding (PF(6))(-) and (BF(4))(-) salts and shows the important effects of aggregation on the observed luminescence.     

Chains, ladders and sheets of d metal–organic polymers generated from the flexible bipyridyl ligands

By use of the three-layer diffusion method, reactions of flexible bipyridyl ligands (4,4′-bpp or 3,3′-bpp) with M(II) salts (M = Zn, Cd) and multi-carboxylate ligands resulted in the formation of four interesting d¹⁰ metal–organic coordination polymers: [Zn(μ-4,4′-bpp)Br₂]_n (1), [Zn(μ-4,4′-bpp)(1,2-bdc)]_n · nH₂O (2), [Zn(μ-3,3′-bpp)(1,3-bdc)]_n · nCH₃OH · 2nH₂O (3) and [Cd(μ-3,3′-bpp)(C₄H₂O₄)]_n · 3nH₂O (4) (4,4′-bpp = 2,2′-bis(4-pyridylmethyleneoxy)-1,1′-biphenylene; 3,3′-bpp = 2,2 ′-bis(3-pyridylmethyleneoxy)-1,1′-biphenylene; bdc=benzenedicarboxylate, C₄H₄O₄ = fumaric acid). Complex 1 has a 2D sheet structure consisting of two unusual zigzag Zn(II) chains which are nearly perpendicular to each other. Complex 2 is comprised of two-leg ladders, in which [Zn(4,4′-bpp)] chains serve as the side rails and 1,2-bdc ligands serve as the cross rungs. In complex 3, every two 1,3-bdc ligands connect the neighbouring Zn(II)-3,3′-bpp dimetallic rings in η¹ coordination modes into an interesting chain structure. Complex 4 consists of an anionic macrocycle-containing cadmium dicarboxylate sheets that are separated by 3,3′-bpp. These d¹⁰ metal complexes exhibit high thermal stabilities and strong luminescence efficiencies.     

Remarkable variations in the luminescence of frozen solutions of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone). Structural and spectroscopic studies of the effects of anions and solvents on Gold(I) carbene complexes

The unusual luminescence behavior of the two-coordinate gold(I) carbene complex, [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone), is reported. Upon freezing in a liquid N(2) bath, the colorless, nonluminescent solutions of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) become intensely luminescent. Strikingly, the colors of the emission differ in different solvents and appear only after the solvent has frozen. Solid [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) is also luminescent, and the luminescence is attributed to the formation of extended chains of gold(I) centers that are connected through aurophilic attractions. Crystallographic studies of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) and [Au[C(NHMe)(2)](2)](BF(4)), which is also luminescent, reveal that both involve extended chains of cations and that the anions are hydrogen bonded to the cations through cation N-H groups. However, these chains differ in the Au...Au separations in each and in the carbene ligand orientations. In contrast, [Au[C(NMe(2))(NHMe)](2)](PF(6)) forms a colorless, nonluminescent solid, and in that solid there are no Au...Au interactions, a factor which supports the contention that aggregated species are responsible for the luminescence of [Au[C(NHMe)(2)](2)](PF(6)) x 0.5(acetone) in the solid state and in frozen solutions.     

Catalytic palladium nanoparticles supported on nanoscale MOFs: a highly active catalyst for Suzuki–Miyaura cross-coupling reaction

Pd nanoparticles have been successfully supported on nanoscale metal-organic frameworks (NMOFs) by using a simple and effective microwave-assisted impregnation process. The resulting composite, representing as a highly active NMOFs supported metal nanoparticles catalyst for the Suzuki cross-coupling reaction between aryl/heteroaryl halides and arylboronic acids, is well characterized, and its high activity and good recyclability are discussed in details. It reveals that, compared to the corresponding bulk MOFs and conventional active carbon materials, nanoscale MOFs as novel support materials for heterogeneous catalysts can exhibit superior performance in the catalytic reactions.     

A new coding scheme of QC-LDPC codes for optical transmission systems

Based on Galois Field (GF(q)) multiplicative group, a new coding scheme for Quasi-Cyclic Low-Density Parity-Check (QC-LDPC) codes is proposed, and the new coding scheme has some advantages such as the simpler construction, the easier implementation encoding, the lower complexity of the encoding and decoding, the more flexible adjustment of the code length as well as the code rate and so forth. Under the condition of considering the characteristics of optical transmission systems, an irregular QC-LDPC (3843,3603) code to be suitable for optical transmission systems is constructed by applying the proposed new coding scheme. The simulation result shows that the net coding gain (NCG) of the irregular QC-LDPC (3843,3603) code is respectively improved 2.14 dB, 1.19 dB, 0.24 dB and 0.14 dB more than those of the classic RS (255,239) code in ITU-T G.975, the LDPC (32640,30592) code in ITU-T G.975.1, the regular SCG-LDPC (3969,3720) code constructed by the Systematically Constructed Gallager (SCG) coding scheme and the regular QC-LDPC (4221,3956) code at the bit error rate (BER) of 10-8. Furthermore, all the five codes have the same code rate of 93.7%. Therefore, the irregular QC-LDPC (3843,3603) code constructed by the proposed new coding scheme has the more excellent error-correction performance and can be better suitable for optical transmission systems.     

Synthesis of Stimuli-responsive Nanoparticles by Solution Polymerization

In this study, stimuli-responsive nanoparticles were prepared by solution polymerization. Two synthesis routes are proposed to synthesize the particles, the monomer route and the polymer/monomer route. For the monomer route, pH and thermal sensitive nanoparticles were synthesized from acrylic acid and N-isopropylacrylamide. For the polymer/monomer route, the pH sensitive nanoparticles were synthesized from chitosan and acrylic acid. The effect of reaction time, initiator concentration and agitation rate on the particle size and the size distribution were investigated. The stimuli-responsive nanoparticles could be directly blended with other polymers to prepare stimuli-responsive functional membranes.     

准一维电荷密度波材料Ta2NiSe7 的转角及变温拉曼光谱研究

近年来, 低维过渡金属硫族化合物Ta2NiSe7 因其独特的电荷密度波和特殊的拓扑能带结构而引起广泛关注. 本文利用拉曼光谱技术对准一维电荷密度波材料Ta2NiSe7 的声子模式进行了系统研究. 角度依赖的偏振拉曼光谱实验表明室温下可以观测到19 个拉曼峰, 且所有观察到的拉曼模式强度随样品旋转呈周期性变化, 这意味着Ta2NiSe7 具有较高的面内各向异性. 通过群论分析, 我们确定了拉曼峰的具体模式为Ag 和Bg 两种原子振动模式. 在温度依赖的偏振拉曼光谱测量中, 我们在低温下还观察到了新的声子峰, 推测与电荷密度波结构调制引起的晶格畸变有关. 本研究提供了对Ta2NiSe7 声子振动的全面理解, 这可能为进一步研究电荷密度波与声子振动之间的关联提供参考意义.     

三种新型二苯砜氮杂环蕃N,N’-二对甲苯磺酰基-1,m-二氮杂[m.1]对环蕃-n-砜的合成与表征(m＝8,10,12; n＝15,17,19)

以N,N’-二对甲苯磺酰基-4,4’-二氨基二苯砜与二溴代烷为原料, 高度稀释条件下合成了三种新型有硫原子桥连的氮杂环蕃N,N’-二对甲苯磺酰基-1,8-二氮杂[8.1]对环蕃-15-砜(C); N,N’-二对甲苯磺酰基-1,10-二氮杂[10.1]对环蕃-17-砜(D); N,N’-二对甲苯磺酰基-1,12-二氮杂[12.1]对环蕃-19-砜(E). 提供了三种环蕃化合物的合成方法. 用IR, 1H NMR和元素分析证实了新化合物结构. 分析了化合物D的单晶结构数据, 为环蕃化合物的空间结构研究提供了晶体学依据.     

Frameworks Tuned by Different Anions via Charge‐Assisted Weak Hydrogen Bonds

Reactions of Co(ClO₄)₂·6H₂O, Cu(NO₃)₂·3H₂O with 4,4′‐dipyridylsulfide (dps) give rise to coordination polymers {[Co(dps)₂(DMF)₂]·2(ClO₄)·2dps}_n ( 1 ) and {[Cu(dps)₂(DMF)(H₂O)]·(PF₆)·(NO₃)}_n ( 2 ) (DMF = formydimethylamine), respectively. X‐ray diffraction analyses reveal that compound 1 has a one dimensional (1D) chain structure, whereas compound 2 is built of the non‐interpenetrating wave‐like (4, 4) nets. Close inspection of the abundant charge‐assisted weak hydrogen bonds (C‐H···X, X = O, F) between the anions and frameworks in these compounds reveals that the appearance of anion may have a subtle effect on the framework topology. Furthermore, quite few examples of framework holding two different anions only via weak effects as 2 were observed in coordination polymers.