正丁基苝四羧酸二酰亚胺的晶型和性能研究

文章合成了N,N'-二正丁基苝四羧酸二酰亚胺,并纯化、调晶,进行了IR、元素分析、X射线等测定.分析该化合物在DMF中的紫外光谱(最大吸收波长524.80 nm)、荧光光谱(最大发射波长539.0 nm)、Stokes位移(数值15 nm)等光谱性质.在400～700 nm范围内,α晶型薄膜紫外-可见吸收出现很强的吸收峰,且由β型变为α型,最大吸收波长有明显的红移(545 nm变为580 nm).X射线粉末衍射也反映出α晶型的2θ在26.0°处衍射峰CPS为2 508,β型在25.2°为1 891.α,β晶型作为电荷产生材料制得的功能分离型有机光导体,在光源滤波波长λ=532 nm曝光下,测得含α,β感光体达到饱和电位的时间分别为46,93.98 s,光衰电位(5.3千伏电压负充电电晕,1～2 s后的表面电位)分别为727和525 V,半衰曝光量分别为4.32,4.34μJ·cm-2,残余电位分别为30和45 V等光导性能数值.     

Melt-polymerizable bisimido-bisphthalonitriles containing silicon,fluoro, and ether groups: Synthesis,characterization, and NMR study

Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (¹H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers.     

High performance liquid chromatographic separation of dipeptide and tripeptide enantiomers using a chiral crown ether stationary phase

A chiral stationary phase (CSP) based on (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was evaluated for the direct resolution of the enantiomers of dipeptides and tripeptides. The type and concentration of the acid and the methanol content were optimized with regard to retention time and resolution using Ala-Phe as model peptide. A mobile phase consisting of 10 mM sulfuric acid in 70% aqueous methanol was applied to the separation of a set of 16 structurally diverse dipeptides and tripeptides. Generally, the configuration of the amino acid at the N-terminus determined the enantiomer elution order. With a few exceptions the LL- and LD-enantiomers interacted stronger with the CSP compared to the corresponding DD- or DL-enantiomers. The experimental conditions also allowed the simultaneous separation of all four stereoisomers of Ala-Phe. Addition of ammonium sulfate generally reduced retention times and enantiomer resolution. Addition of triethylamine as modifier led to an overall increase of the retention times while the resolution did not show a general trend, increasing in the case of Ala-Ala but decreasing in the case of Ala-Phe.     

Influence of the Size of Aromatic Chelate Ligands on the Structures of Cadmium(II) Tetracarboxylates Polymers: From 2D Layered Network to 3D Metal‐Organic Framework

To determine the influence of the size of the aromatic chelate ligands on the frameworks of metal tretracarboxylate polymers, two new coordination polymers [Cd(btc)_0.5 (2,2′‐bpy)] ( 1 ) and [Cd(btc)_0.5(phen)]·H₂O ( 2 ) (H₄btc = biphenyl‐3,3′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under similar hydrothermal conditions. In complex 1 , the dimeric Cd₂ units are linked by bridging btc^4? ligand to form a 2D layered network, whereas complex 2 possesses a 3D metal‐organic framework consisting of the dimeric Cd₂ units. The differences of two metal‐organic frameworks demonstrate that the size of the rigid aromatic chelate ligands have an important effect on the structures of their complexes. Additionally, the two complexes show strong fluorescence in the solid state at room temperature.     

Polyoxometalates as Inorganic Building Blocks of Multifunctional Molecular Materials

The use of polyoxometalates (pOM's) as inorganic component in the synthesis of new molecular hybrid materials is presented. Here we show that the combination of organic molecules of the tetrathiafulvalene (TTF) type or perylene (per) with POM's yields new radical salts with unprecedented structures that present interesting magnetic and/or electrical properties or coexistence of both. The first true metallic radical salt containing a POM has been prepared and characterized. We also describe the recent results obtained by combining magnetic POM's with the organometallic cation decamethylferrocene.     

基于芳香四羧酸构筑的两种配位聚合物的荧光及磁性质（英文）

在溶剂热条件下,基于芳香四羧酸合成了2种新颖的配位聚合物:{[Zn2(tptc)(1,4-bimb)2]·H2O}n(1)和{[Ni(tptc)0.5(1,2-bimb)(H2O)]·H2O}n(2),其中,tptc为对-三联苯-3,3″,5,5″-四羧酸,1,4-bimb为1,4-二(咪唑-1-亚甲基)苯,1,2-bimb为1,2-二(咪唑-1-亚甲基)苯。结构分析表明,1为三维结构,拓扑符号为(86);2为二维层状网络,通过氢键相互作用进一步扩展为三维超分子结构。此外,我们还研究了1对阳离子、阴离子的荧光感应以及2的磁性质。     

Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces

Terpyridine‐substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl‐crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn²⁺ ions allowed for layer‐by‐layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid‐state dye‐sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed.     

2,9-Diazadibenzoperylene and 2,9-Dimethyldibenzoperylene-1,3,8,10-tetratriflates: Key to Functionalized 2,9-Diazaperopyrenes

The synthesis of 2,9-diaza-1,3,8,10-tetratriflato-dibenzoperylene (DDP 3 a ) and corresponding 2,9-dimethyl-1,3,8,10-tetratriflato-dibenzoperylene (DBP 3 b ) has been developed at multigram scale via reduction of one of the industrially most important high-performance dyes, perylene-3,4,9,10-tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2,9-diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O-phosphanyl substituents. The influence of electron-donating substituents (OSiMe₃, OPt-Bu₂, N-piperidinyl), electron-withdrawing (OTf, 3,5-bis-trifluoromethyl-phenyl), and of electron-rich π-conjugated (2-thienyl, 4-tert-butylphenyl, trimethylsilyl-ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD-DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI.