Li+-templated complexation of cylindrical macrotricyclic host with naphthalene diimide: Cation-controlled switchable complexation processes

Anthracene-based cylindrical macrotricyclic polyether (1) containing two dibenzo-30-crown-10 cavities has been proved to be an efficient host for the templated complexation with N,N’-dipropyl-1,4,5,8-naphthalenetetracarboxylic diimide in the presence of lithium ions in both solution and solid state. Host 1 could also form 1:1 complex with the bispyridinium salt with two β-hydroxyethyl groups in solution and in the solid state. Moreover, it was also found that the switchable complexation processes between the macrotricyclic host and two different kinds of guests could be chemically controlled by the addition and removal of lithium ions.     

Synthesis and in vitro activities on anti-platelet aggregation of N,N’-di(2-substituted-phenyl)-4-methoxyisophthalamides and benzene- 1,3-disulfonamides

On the propose of searching for the SAR and obtaining novel antiplatelet aggregating drugs,we have described the synthesis procedure and the activities in vitro on antiplatelet aggregation of two series of derivatives,which contain both 18 N.N’-di(2- substitutedphenyl)-4-methoxyisophthalamides(2a-2r) of the 2 series and nine N,N’-di(2-substitutedphenyl)-4-methoxybenzene- 1,3-disulfonamides(3a-3i) of the 3 series.The results showed that three compounds 2e,2i and 3g emerged as significant activities of antiplatelet aggregation,superior to two reference drugs picotamide and aspirin,and eight compounds 2j,2k,21,2o,2p,2q,2r and 3i merely superior to picotamide.The preliminary SAR shows that it is favorable for the 2 series to increase the activities via the steric hindrance substituents attached to the two side chain benzene rings at 2-positions.And the arylamides of the 2 series have better the activity values than the arylsulfonamides of the 3 series respective except for 3b and 3g.On the contrary,electrostatic factors would not contribute evidently to the activities of the two series.The structures of 15 compounds newly synthesized have been established by MS and ~1H NMR and been first reported in this paper.     

Effect of Fluorination on Aggregate Structure of Perylene Diimide

The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N‘-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.     

(Ph2N)2Sm(THF)4与偶氮苯的反应：[(Ph2N)(DME)Sm]2(μ-η2:η2-N2Ph2)2的合成、X－光结构和催化行为

Reaction of divalent (Ph2N)2Sm(THF)4 with 1 equiv, of azobenzene in THF and then crystallization of the product in DME-Et2O mixed solvent produced the complex of [(PhEN)(DME)Sm]E(μ-η^2:η^2-N2Ph2)2 (1) in 65.0% yield. In complex 1, azobenzene molecules were reduced to be dianionic Ph2N2^2- ligands, bridging two samarium ions in two η^2:η^2 fashions. One samarium ion was bonded to a DME molecule and a diphenyl amido ligand besides two Ph2N2^2- ligands. The unusual Ln-η^2-arene close interaction was found for the first time for diphenyl amido lanthanides. Complex 1 could catalyze the polymerization of methyl methacrylate and acrylonitrile     

High-capacity Hydrogen Storage on Novel Sandwich- like Binuclear Compounds： N4-M2-N4 （M - Sc and Ti）

With respect to the first principle calculations, we predicted that two pairs of transition metals (e.g., Sc2 and Ti2) can be interbedded between two tetranitrogen rings to form two sandwich-like binuclear complexes respectively (e.g. N4Sc2N4 and N4Ti2N4). These two complexes can adsorb up to eight and ten hydrogen molecules, corresponding to a gravimetric storage capacity of 7.7 and 9.9 wt%, respectively. These sandwich-type complexes proposed in this work are favorable for reversible adsorption and desorption of hydrogen at ambient conditions. The results are helpful for the development of a new class of high-capacity hydrogen-storage media.     

Self-assembled helical nanostructures from an asymmetrical perylene diimide

An asymmetrical perylene diimide 3, N-（4-methoxyphenyl）-N＇-（4-nitrophenyl）-perylene-3,4,9,10-tetracarboxylic diimide, was synthesized, and its self-assembly and dissociation behaviors in chloroform was studied in detail by UV-vis and fluorescence spectroscopies. The resulting unique helical nanostructures from 3 were proposed to be self-assembled via the cooperative actions of π-π stacking, steric hindrance and electrophile-nucleophile type pairing.     

氢键和供体－受体相互作用驱动的酰肼异体二聚体组装

A new series of hydrogen bonding-driven heterodimers have been self-assembled in chloroform from hydrazide-based monomers. Additional intermolecular donor-acceptor interaction between the electron-rich bis（p-phenylene）-34-crown-10 unit and the electron-deficient naphthalene diimide unit has been utilized to increase the stability of the dimmers, and pronounced cooperativity of the two discrete non-covalent forces to stabilize the dimer has been revealed by the quantitative ^1H （2D） NMR and UV-Vis experiments.     

The catassembled generation of naphthalene diimide coordination networks with lone pair-π interactions

Catassembly is a new concept in molecular assembly that is analogous to catalysis in chemical synthesis. However, for most molecular-assembled processes, the catassembler contributions are rather inconspicuous due to the low activation barriers. As a result, few systems dealing with the catassembly are available until now. In this paper, we report that naphthalene diimide coordination networks are formed under the catassembly of lone-pair-bearing catassemblers(e.g., N,N-dimethylacetamide, N-methylpyrrolidin-2-one). During such molecular assembly, a stable transition state between the electron-deficient naphthalene diimide tectons and catassemblers via the less common lone pair-π interactions was observed, which is supposed to play the key role in the enhancement of coordination abilities of organic tectons and thus formation of the final coordination networks.     

α-proton deuterium exchange of five-coordinate bicycloazastannoxides catalyzed by Et_3N

The five-coordinate bicycloazastannoxides (1—6) in the presence of Et_3N has been investigated by~1H NMR spectrograph. It has been found that the deuterium exchange of αCH of five-coordinate bicycloazastannoxides with CD_3OD takes place, which is catalyzed by Et_3N. In the presence of Et_3N (2μL), the apparent rate constants (k_(obs)) for the deuterium exchange in CD_3OD is determined by~1H NMR method, and the value of k_(obs) is in the range of (2.05--10.8)×10~(-4) s~(-1). The effect of the substitutes on the rates and the kinetic mechanism are discussed.     

Subsolidus binary phase diagram of the bilayer compounds [n-C_nH_(2n+1)N(CH_3)_3]_2ZnCl_4(n = 16, 18)

The bilayer compounds[n-CnH2n+1N(CH3)3]2Zn Cl4(n=16,18)experience solid-solid phase transition within the temperature range of 310 to 340 K.The low-temperature crystal structures of the pure compounds are characteristic of the piling effect in which a 2D macro-anion Zn Cl42- is sandwiched between two alkylammonium layers.These layers become conformationally disordered in the high-temperature phases.The structures can alternatively be viewed as a double layer of alkylammonium ions between Zn Cl42- sheets and can be considered as crystalline models of lipid bilayers.The experimental subsolidus binary phase diagram of[n-C16H33N(CH3)3]2Zn Cl4-[n-C18H37N(CH3)3]2Zn Cl4 has also been established over the whole composition range by differential scanning calorimetry(DSC)and X-ray diffraction.In the phase diagram,one intermediate compound[n-C16H33N(CH3)3][n-C18H37N(CH3)3]Zn Cl4 at WC16C3Zn%47.50 and two eutectoid invariants points at WC16C3Zn%35.10 and75.70 were observed;the respective temperatures of the two eutectoids are 320±1 and 315±1 K.In addition,there are three noticeable solid solution ranges in the phase diagram:α-phase at the left,β-phase at the right,andγ-phase in the middle.     

Protonation and Dehydrogenation During the Multiphoton Ionization of the Cluster: C_4H_5N(H_2O)_n

Proton transfer process in hydrogen-bonded clusters has attracted great interest of many chemists in physical chemistry and biochemistry1-5. Pyrrole (C4H5N) is one of the building blocks of some important biomolecules6. And pyrrole is a compound of five-membered hetero-cyclic aromatic ring, in which a lone pair of electrons offered by the N atom and the two double bonds form a delocalized big ( bond. In this paper we report on the observations for the cluster system pyrrole-water by use of a…     

Azo Bond Reduction of N,N＇,diaryl Adipyl Bis-azo Compounds with Hydrazine Hydrate

Reduction of a series of N,N'-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,N'-diaryl adipyl dihydrazine. The results show that hydrazine hydrate can selectively reduce azo bonds with other potential reducible bonds intact in the N,N'-diaryl adipyl bis-azo compounds. The yields are high up to 92% under mild reaction conditions. According to the previous reports, this reduction process was attributed to an indirect reduction mechanism through an intermediate diimide.     

8.0% Efficient all-polymer solar cells based on novel starburst polymer acceptors

The polymer N2200, with its π-conjugated backbone composed of alternating naphthalene diimide(NDI) and bithiophene(DT)units, has been widely used as an acceptor for all-polymer solar cells(all-PSCs) owing to its high electron mobility and suitable ionization potential and electron affinity. Here, we developed two naphthalene diimide derivatives by modifying the molecular geometry of N2200 through the incorporation of a truxene unit as the core and NDI-DTas the branches. These starburst polymers exhibited absorption spectra and molecular orbital energy levels that were comparable to N2200. These copolymers were paired with the wide-bandgap polymer donor PTz BI-O to fabricate all-polymer solar cells(all-PSCs), which displayed impressive power conversion efficiencies up to 8.00%. The improved photovoltaic performances of all-PSCs based on these newly developed starburst acceptors can be ascribed to the combination of increased charge carrier mobilities, reduced bimolecular recombination, and formation of more favorable film morphology. These findings demonstrate that the construction of starburst polymer acceptors is a feasible strategy for the fabrication of high-performance all-PSCs.     

ESR Investigation of Single Crystal of (Bu_4N)_2[Cu/Pd(dmit)_2]

By incorporating (Bu4N)2[Cu(dmit)2] with the diamagnetic host complex (Bu4N)2[Pd (dmit)2], single crystal of (Bu4N)2[Cu/Pd(dmit)2] is obtained. Its ESR spectra of various orientations are recorded. The principal values of g and A tensors and their direction cosines are computed using a least-squares fitting procedure, and based on which the molecular orbital of unpaired electron in [Cu(dmit)2]2- is described. The essence of the two magnetically non-equivalent sites is also revealed.     

THE SIMULTANEOUS DISCHARGES OF TWO NEURONS IN N. Pf AND RF AND THE INFLUENCES ON THEM BY STIMULATING CENTRAL GRAY MATTER

This paper employs the method of simultaneous recording of the electric discharges oftwo neurons with two microelectrodes to study the interrelationship of simultancous electricactivities of pain excitation neurons (PEN) and pain inhibition neurons (PIN) in N. parafas-cicularis (Pf) of thalamus and reticular formation (RF) of midbrain in 42 rats. The resultsprove: (i) There are both PEN and PIN in RF in midbrain and they act coordinately;(ii) noxious messages may simultaneously act on PEN and PIN in N. Pf and RF, and thereciprocal coordination of electric activities of these two kinds of neurons is very obvious;(iii) stimulating central gray matter or injecting morphine may weaken the activities ofPEN simultaneously, with the opposite effects on PIN.     

Synthesis of a novel perylene diimide derivative and its charge transfer interaction with C_(60)

A novel organic electron acceptor, N,N′-dipyrimidinyl-3,4,9,10-perylene-tetracarboxylic diimide (DMP), was designed and synthesized. The molecular structure was characterized by FTIR spectrum and elemental analysis. By cyclic voltammetry measurements, DMP was found to possess a lower LUMO energy level than N,N′-diphenyl-3,4,9,10-perylene-tetracarboxylic diimide due to the stronger electron-withdrawing pyrimidinyl group than the phenyl group. Fluorescence quenching is observed in a dual-layer film consisting of a DMP layer and a C60 layer and was attributed to the charge transfer at the interface due to the energy level offset between DMP and C60.     

Isothianaphthene diimide: an air-stable n-type semiconductor

Herein, we propose a new strategy to develop air-stable n-type organic semiconductors with non-classical thiophene aromatic diimide derivatives by replacing aromatic naphthalene with a heteroaromatic isothianaphthene core. We designed and successfully synthesized the isothianaphthene core based diimide material, N,N′-bis(n-hexyl)isothianaphthene-2,3,6,7-tetracarboxylic acid diimide(BTDI-C6) as an n-type semiconductor. Compared to N,N′-bis(n-hexyl)naphthalene-1,4,5,8-tetracarboxylic acid diimide(NDI-C6), BTDI-C6 possesses a deeper LUMO energy level of-4.21 eV, which is 0.32 eV lower than that of NDI-C6. Both molecular modelling and experimental results elucidated that organic thin film transistors(OTFTs)based on both of these materials exhibit comparable mobilities; however, the threshold voltage of BTDI-C6 based device(+7.5 V) is significantly lower than that of NDI-C6 based counterpart(+34V). Moreover, the low-lying LUMO energy level of BTDI-C6 ensures excellent air-stability which is further validated by the device performance. In addition, BTDI-C6 shows high luminescence while NDI-C6 is not luminescent at all in solution, which reveals the potential application of our newly synthesized material in n-type light-emitting transistors.     

CRYSTAL STRUCTURE OF N, N'''' -BIS ( 2-METHOXY-1-NAPH-THYLMETHYL)-4,13-DIAZA-18-CROWN-6 POTASSIUM IODIDE

<正> Crystal of N , N'-bis(2-methoxy-l-naphthylmethyl)-4,13-diaza-18-crown-6 potassium iodide diethanol solvate[(C36H46N2O6)K]+I- · 2C2H5OH (Mr = 860. 47) is orthorhombic with space group Pcab, a = 17. 531(5), 6 = 21. 149(8), c = 23. 060(4)(?). F=8550. 00(?)3, Z = 8, F(000) = 3167. 64 and Dc=1. 337g/ cm3, μ = 8. 74cm-1, R = 0. 057. In the title complex, the donor atoms of the macro-ring are arranged in a twisted boat conformation. The potassium ion is octa-coordi-nated with four oxygen and two nitrogen atoms of the macro-ring and two oxygen atoms of the two side arms at the same side to form a distorted hexagonal bipyramid.     

Syntheses and Crystal Structures of the First Row Transition Metals with 1,6-Bis(2'-pyridyl)-2,5-dithiahexane

Six first row transition metal complexes with 1,6-bis(2′-pyridyl)-2,5-dithiahexane(Py_2S_2), namely, MnPy_2S_2Cl_2(1), FePy_2S_2Cl_2(2), Co Py_2S_2Cl(3), CoPy_2S_2(SCN)_2(4), NiPy_2S_2(SCN)_2(5) and NiPy_2S_2(N_3)_2(6), have been synthesized. A mixture of MCl_2·x H_2O(M = Mn, Co) in MeOH(FeCl_2·4H_2O in MeCN) and the stoichiometric amount of Py_2S_2 was stirred for 4 h at room temperature, then these aiming products 1, 2 and 3 could be obtained by purification. A mixture of MPy_2S_2Cl_2(M = Co, Ni) in MeOH and two equivalents of KSCN or NaN_3 was stirred for 4 h at room temperature. After that, complexes 4, 5 and 6 could be got by purifying. For 1, 2, 3, 4 and 5, the metal centers are hexa-coordinated in a similar distorted octahedral geometry and the crystal structures have the same space group Pbcn. The crystal structure of compound 6 belongs to monoclinic with space group P21/c. The coordinated atoms around M(Ⅱ) are two pyridyl N atoms(N(1) and N(2)), two thioether S atoms(S(1) and S(2)) and two chloride ions(Cl(1) and Cl(2)) in compounds 1, 2, and 3, but in 4, 5, and 6, two chloride ions(Cl(1) and Cl(2)) are replaced by another two N atoms from N_3~– or NCS~–.     

CRYSTAL AND MOLECULAR STRUCTURE OF N, N-PLATINUM-DIETHYL-DICHLORIDEDI-L-ASPARTATE

This paper reports the crystal and molecular structure of title compound. 3978 three-dimensional independent reflections were collected by Syntex R3 four circle diffractometer. The crystal is monoclinic with space group P2_1, a=8.074(1), b=11.309(4), c=27.793(9), β=106.84°(2), Z=4. The molecular formula is Pt(C_8 H_(15)O_4N)_a Cl_2. The crystal structure was solved by Patterson method and refined by block matrix least squares refinement techniques. The final R factor is 0.039.The result of crystal structure analysis shows that Pt(Ⅱ) has a dsp~2 hybrid orbital and square coordination. Two C1 atoms are located oppositely to two diethyi-dichloride-di-L-aspartare. N atoms have sp~3 tetrahedral hybrid configurations and form the coordinate bonds with Pt(Ⅱ) atom using their lone pair electrons. By reason of molecular packing and due to the formation of inner hydrogen bonds in the complex molecule, the configuration of L-aspartic acid in the title complex is more twisted than that of L-and DL-aspartic acid