Synthesis, Characterization and Crystal Structure of （Z）-1-[2-（Triarylstannyl）vinyl]-1-indanols and Their Arylhalostannyl Derivatives

(Z)-1-[2-(Tri-o-tolylstannyl)vinyl]-1-indanol (1) and (Z)-1-[2-(tri-p-tolylstannyl)vinyl]-l-indanol (2) were synthesized by the addition reaction of 1-ethynylindanol with tri-o-tolyltin and tri-p-tolyltin hydride. The aryl groups in compound 1 and 2 were substituted by Br2 or I2 to yield monohalide derivatives (3-6). The compounds 1-6 were characterized by elemental analysis, ^1H NMR and FT-IR spectroscopy. The crystal structures of 1, 2 and 4 have been determined by single crystal X-ray diffraction analysis. The Sn atom in 1 and 2 exhibits a tetrahedral geometry distorted towards trigonal bipyramid due to a weak intramolecular interaction between Sn and the hydroxyl O atoms [0.2839(4) nm and 0.2744(5) nm], while the Sn atom in 4 adopts a trigonal bipyramidal geometry with a significant O→Sn(1) interaction [0.2552(5) nm].     

Flavin Derivatives with Tailored Redox Properties: Synthesis,Characterization, and Electrochemical Behavior

This study establishes structure–property relationships for four synthetic flavin molecules as bioinspired redox mediators in electro‐ and photocatalysis applications. The studied flavin compounds were disubstituted with polar substituents at the N1 and N3 positions (alloxazine) or at the N3 and N10 positions (isoalloxazines). The electrochemical behavior of one such synthetic flavin analogue was examined in detail in aqueous solutions of varying pH in the range from 1 to 10. Cyclic voltammetry, used in conjunction with hydrodynamic (rotating disk electrode) voltammetry, showed quasi‐reversible behavior consistent with freely diffusing molecules and an overall global 2e^?, 2H⁺ proton‐coupled electron transfer scheme. UV/Vis spectroelectrochemical data was also employed to study the pH‐dependent electrochemical behavior of this derivative. Substituent effects on the redox behavior were compared and contrasted for all the four compounds, and visualized within a scatter plot framework to afford comparison with prior knowledge on mostly natural flavins in aqueous media. Finally, a preliminary assessment of one of the synthetic flavins was performed of its electrocatalytic activity toward dioxygen reduction as a prelude to further (quantitative) studies of both freely diffusing and tethered molecules on various electrode surfaces.     

Synthesis and Structural Characterization of Pyridine-2,6-dicarboxamide and Furan-2,5-dicarboxamide Derivatives

Derivatives based on pyridine-2-6- and furan-2,5-dicarboxamide scaffolds reveal numerous chemical properties and biological activities. This fact makes them an exciting research topic in supramolecular and coordination chemistry and in discovering new pharmacologically-active compounds. This work aimed to obtain a series of symmetrical pyridine-2-6- and furan-2,5-dicarboxamides through a condensation reaction of the appropriate acyl chlorides and aromatic amides. Successful syntheses were confirmed with NMR spectroscopy. We solved their crystal structures for seven compounds; two pyridine and five furan derivatives. Based on our crystallographic studies, we were able to indicate supramolecular features of the crystals under investigation. Additionally, Hirshfeld surface analysis allowed us to calculate a distribution of intermolecular contacts in the dicarboxamide crystals.     

Tetrasubstituted Peropyrenes Formed by Reductive Aromatization: Synthesis,Functionalization and Characterization

The chromophore class of 1,3,8,10-tetrasubstituted peropyrenes was effectively synthesized from peropyrenequinone via a Zn-mediated reductive aromatization approach. In one step, a symmetric functionalization of the peropyrene backbone introducing silylethers ( 2 , 3 ), pivaloyl ( 4 ), triflyl ( 5 ) and also phosphinite ( 6 ) groups was established. Furthermore, the potential of using 4 and 5 in transition metal catalysed cross couplings was explored leading to 1,3,8,10-tetraaryl ( 8 - 11 ) and tetraalkynyl ( 7 ) peropyrenes. The influence of various substituents on the optoelectronic properties of these π-system extended peropyrenes was investigated in solid state by means of X-ray crystallography, in solution by means of UV-Vis and fluorescence spectroscopy and by their redox properties studied via cyclic voltammetry. By comparison with DFT and TD-DFT calculations, it could be elucidated that introduction of a broad variety of substituents in such versatile one or two step procedures leads to peropyrenes with easily tunable HOMO and LUMO energies ranging in a gap window of 0.8 eV. The frontier molecular orbital energies identify the target molecules as promising candidates for hole transporting semiconductors.     

Spectral and Electrochemical Investigation of Intercalations of Adrenaline and CT－DNA

A strong interaction between double stranded calf-thymus DNA (ds-DNA) and adrenaline in solution, but no interaction between single stranded calf-thymus DNA (ss-DNA) and adrenaline was observed by the use of UV-visible spectroscopy and voltammetric techniques. It is suggested that the interaction leads to an intercalation of adrenaline molecules into the groove of ds-DNA and the formation of ds-DNA (adrenallne)n complex. The binding site size of the interaction of adrenaline with CT-DNA in nucleotide phosphate [ NP] has been determined as 25. The interaction of different concentration adrenaline with DNA modified GCE shows that the DNA modified GCE can be a good tool to detect lower concentration adrenaline.     

Synthesis and Characterization of Conducting Copolymers of Thiophene Derivatives

Electrochemical copolymerizations of N¹,N²-bis(thiophen-3-ylmethylene)benzene-1,2-diamine (TMBD), 4-methyl-N¹,N²-bis (thiophen-3-ylmethylene)benzene-1,2-diamine (MTMBD) and 4-nitro-N¹,N²-bis(thiophen-3-ylmethylene)benzene-1,2-diamine (NTMBD) with 3,4-ethylenedioxy thiophene (EDOT) were carried out in CH₃CN/LiClO₄ (0.1 M) solvent–electrolyte couple via potentiodynamic electrolysis. The resulting copolymers were characterized by cyclic voltammetry (CV), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The conductivity measurements of copolymers and PEDOT were carried out by the four-probe technique.     

Synthesis,Characterization, and Structure of Some New Substituted 5,6-Fused Ring Pyridazines

Pyridazines are an important class of heterocyclic compounds as a result of their materials and commercial applications. The synthesis of 5,6-fused ring pyridazines 2a–h from 1,2-diacylcyclopentadienes (fulvenes) 1a–h is described herein. This route was quite general, and features an efficient and convenient two-step synthesis of a series of 5,6-fused ring 1,2-disubstituted pyridazines using enolized 1,2-disubstituted fulvenes in a methanolic solution of hydrazine. Full characterization of newly formed fulvene 1e and pyridazines 2a–h are reported. Single-crystal X-ray analysis confirms the molecular structure of pyridazine 2f, which displayed the expected pyridazine fused to the cyclopentadienyl moiety. Adding to their real world capabilities in electronic devices, compounds 2a–h display reasonably high stability in solution and in air at room temperature.

Synthesis and Electronic Properties of Novel 5,7-Diazapentacene Derivatives

A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes.     

对-氢醌金属配合物：合成，结构及电化学性质

A new Chromium(Ⅲ) complex, [Cr(Hcah)(H₂O)₂]·2H₂O, where H₄cah=2-[N,N-bis(carboxymethyl)aminome-thyl] hydroquinone (H₄cah), has been synthesized and characterized using X-ray diffraction single crystal structure determination, IR and elemental analysis. The complex belongs monoclinic, space group P2₁/c, with a=0.792 05(4) nm, b=1.008 63(6) nm, c=1.920 40(10) nm, β=93.069(4)°, V=1.531 98(14) nm³, and Z=4. The cyclic voltametric analysis shows that the electron transfer in the electrode reaction is irreversible for Cr(Ⅲ)/Cr₂O₇^2- and Cr(Ⅲ)/Cr(Ⅱ) redox couples while reversible for process of interchange from p-Hydroquinone to p-semiquinones. CCDC: 666208.     

Synthesis and Characterization of Novel Mercapto-end Ferrocenyl Derivatives with Schiff Base Linkage

Novel ferrocenyl derivatives of p-(10-mercaptodecyloxy)benzal 4-ferrocenylaniline have been prepared and characterized by element analysis,HNMR,and FAB=MS,Cyclic voltammetry has been used to characterize the self-assembled monolayers formed from the compounds on the gold electrodes.     

2,2'-二苯并噁唑衍生物的合成和光性能研究

合成了16种2,2-二苯并(口恶)唑衍生物,测定了化合物的熔点、红外光谱、紫外吸收光谱、荧光发射光谱以及荧光量子产率,与1,4-二(苯并(口恶)唑1′,3′-基-2′)苯和1,4-二(苯并(口恶)唑-1′,3′-基-2′)乙烯衍生物进行了比较,讨论了它们之间光谱特性的差异.     

Synthesis,Structures, and Properties of Branched Oligogermanes

Abstract

We have employed the hydrogermolysis reaction for the preparation of rare branched oligogermanes, and have obtained for the first time the X-ray crystal structures of several branched tetragermanes, including (Ph₃Ge)₃GePh, (Ph₃Ge)₃GeH, and (Ph₃Ge)₃GeX (X = Cl or Br). We also have at our disposal branched tetragermanes having the formula (EtOCH₂CH₂Bu ⁿ ₂Ge)₃GePh, where the ethoxyethyl substituent serves as a protecting group for a germanium–hydride active site. These reagents have been employed for the stepwise synthesis of higher branched systems having up to 13 bonded germanium atoms in the oligomer backbone. The synthesis, structures, and physical characteristics of these systems are described.

GRAPHICAL ABSTRACT     

齐聚噻吩衍生物在溶液中的光物理和电化学性质

The photophysical and electrochemical properties of a family of oligothiophene derivatives in solution werestudied.It was found that the cyano and the vinyl group could increase fluorescence yield in solution,while theformyl and carboxyl group could decrease energy gap.With increasing the chain length of thiophene ring,the oxi-dation potential could be decreased.     

新型卟啉衍生物的合成、结构表征和电化学性质的研究

以合成的[5-(4-溴苯基)-10,15,20-三苯基卟啉]锌为底物,通Stille偶联的方法合成5-(4’-氨基-4-联苯基)-10,15,20-三苯基卟啉,[5-(4’-氨基-4-联苯基)-10,15,20-三苯基卟啉]锌配合物以及[5- (4’-甲硫基-4-联苯基)-10,15,20-三苯基卟啉]锌配合物。并用Uv,‘H NMR, IR, Ms, Fs等表征确证了该系列配合物的结构,并用循环伏安法对以上部分产物进行了电化学性质的研究.     

Synthesis, Crystal Structure and Electrochemical Studies of Two Novel Zn(II) Complexes of Phthalic Acid and Imidazole Derivatives

Two novel coordination polymers [Zn(pa)(vim)2]n (1) and [Zn(pa)(eim)2]n (2) (pa＝phthalic acid dianion, vim＝1-vinyl-1H-imidazole, eim＝1-ethyl-1H-imidazole) have been synthesized and their structures characterized by X-ray single crystal diffractometry and elemental analysis. Both of the complexes consist of [Zn(L)2] (L＝vim for 1; eim for 2) entities linked into polymeric zigzag chains along the crystallographic c-axis by bridging phthalate anions in the μ2-1,2 coordination mode. The coordination around each Zn(II) atom is tetrahedral. There are only van der Waals interactions between the chains in 1, while the three-dimensional network in 2 is assembled by C—H…O contacts. The electrochemical studies reveal that redoxes of Zn2+/Zn in complexes 1 and 2 are irreversible processes.     

1,8‐Naphthalimide‐Substituted BODIPY Dyads: Synthesis,Structure, Properties,and Live‐Cell Imaging

A set of 1,8‐naphthalimide (NPI)‐substituted 4,4‐difluoroboradiaza‐s‐indacene (BODIPY) dyads 1 a – 1 c were designed and synthesized by the Pd‐catalyzed Sonogashira cross‐coupling reaction of ethynyl substituted NPI 1 with the meso‐, β‐, and α‐halogenated BODIPYs a , b , and c , respectively. The BODIPY 1 c exhibits redshifted absorption, which suggests better electronic communication with substitution at the α‐position of BODIPY compared with at the meso and β positions, which was further supported by time‐dependent DFT calculations. The optical band gap follows the order 1 a > 1 b > 1 c . The single‐crystal X‐ray structures of dyads 1 a – 1 c are reported, which reflect planar orientations of the BODIPY units with respect to the NPIs. The DFT‐optimized structures show good correlation with the experimental data obtained from the single‐crystal X‐ray structures. The packing diagram of 1 a shows a sheet‐like arrangement, 1 b forms a ladder‐like structural motif, and 1 c forms a complex 3D structural arrangement. The dyads 1 a – 1 c show low cytotoxicity (IC₅₀>100 μm ). The confocal microscopy studies with HeLa and A375 cells (when treated with dyads 1 a – 1 c ) show that all the dyads easily enter the cell membrane and show significant multicolor intracellular fluorescence covering the entire visible range with clear emissions in blue, green, and red channels.     

Structural diversity in phosphoramidate’s chemistry: Syntheses,spectroscopic and X-ray crystallography studies

Novel phosphorus compounds of bisphosphoramidate, phosphoramidate and phosphoric triamide derivatives were synthesized using the starting materials PCl₅ and POCl₃. The products were then characterized by ¹H, ¹³C, ³¹P, ¹⁹F NMR, IR spectroscopy and CHN elemental analysis. It is noticeable that the reaction of 4-aminobenzamide with PCl₅ in different molar ratios yields different products, bisphosphoramides and phosphoric triamides. Moreover, we were taken by surprise that the interaction of POCl₃ with the first-type aromatic amines gave bisphosphoramidates with P–N–P linkages that exhibited ²J(P,P) ≈ 20.0 Hz in the ³¹P NMR spectra. In fact, two simple one-pot pathways are presented here for the synthesis of new bisphosphoramidates, and to the best of our knowledge these are the first instances of bisphosphoramidates that have been obtained up until now. The structures of compounds I (4-OCH₃–C₆H₄–CH₂–C₉H₁₃–NH₂Cl), 34 and 44 were further determined by X-ray crystallography. All of these structures produced three dimensional polymeric chains through strong- and weak hydrogen bonds. The presence of chiral aminoacidester moieties in the phosphoric triamides lead to chiral molecules that showed two sets of signals for the two groups. Interestingly, in phosphoric triamides containing cyanoacetamide moieties, the existence of aromatic amine substituents on the P atoms created central chiral phosphorus atoms, i.e. the two aromatic groups revealed two sets of peaks in the ¹H and ¹³C NMR spectra, while compounds with aliphatic moieties did not display this effect.     

大环二羰四胺Ni(Ⅱ)单核和Ni(Ⅱ)-Cu(Ⅱ)双核配合物的合成、表征及电化学性质

合成了一种草酰胺桥联大环二羰四胺Ni(Ⅱ )单核配合物 ,并以此为母体合成了Ni (Ⅱ ) -Cu (Ⅱ )双核配合物 .用元素分析、红外光谱、差热分析、紫外光谱、摩尔电导以及循环伏安等测试手段对配合物进行了表征和电化学性质研究 .经分析 ,标题配合物具有草酰胺桥联结构 ,Ni(Ⅱ )处于平面正方场 ,Cu (Ⅱ )处于八面体场中 .循环伏安测试表明此类配合物能稳定Ni(Ⅲ ) .     

Design,Synthesis, Electronic Properties,and X-ray Structural Characterization of Various Modified Electron-Rich Calixarene Derivatives and Their Conversion to Stable Cation Radical Salts

We have designed and synthesized electron-rich calixarene derivatives, which undergo reversible electrochemical oxidation in a well-accessible potential range that allows the ready preparation and isolation of the corresponding cation radicals. Preparation of mono- or tetra-radical cation can be achieved by using stable aromatic cation-radical salts such as MA^+•, MB^+•, and NAP^+• as selective organic oxidants. The cation radicals of calixarenes are stable indefinitely at ambient temperatures and can be readily characterized by UV-vis-NIR spectroscopy. These cation radicals bind a single molecule of nitric oxide within its cavity with remarkable efficiency.