Ethoxy‐substituted Oligo‐phenylenevinylene‐Bridged Organic Dyes for Efficient Dye‐Sensitized Solar Cells

Organic dyes with ethoxy‐substituted oligo‐phenylenevinylene as chromophores were synthesized for dye‐sensitized solar cells (DSSCs), and the detailed relationships between the dye structures, photophysical properties, electrochemical properties, and performances of DSSCs were described. The dye S3O showed broad IPCE spectra in the spectral range of 350–750 nm, and the dye S1P showed solar energy‐to‐electricity conversion efficiency (() of up to 4.23% under AM 1.5 irradiation (100 mW/cm²) in comparison with the reference Ru‐complex (N719 dye) with an η value of 5.90% under similar experimental conditions.     

Assessment of Luminescent Downshifting Layers for the Improvement of Light‐Harvesting Efficiency in Dye‐Sensitized Solar Cells

Luminescence downshifting (LDS) of light can be a practical photon management technique to compensate the narrow absorption band of high‐extinction‐coefficient dyes in dye‐sensitized solar cells (DSSCs). Herein, an optical analysis on the loss mechanisms in a reflective LDS (R‐LDS)/DSSC configuration is reported. For squaraine dye (550–700 nm absorption band) and CaAlSiN₃:Eu²⁺ LDS material (550–700 nm emission band), the major loss channels are found to be non‐unity luminescence quantum efficiency (QE) and electrolyte absorption. By using an ideal LDS layer (QE=100 %), a less absorbing electrolyte (Co‐based), and antireflection coatings, approximately 20 % better light harvesting is obtained. If the absorption/emission band of dye/LDS is shifted to 800 nm, a maximal short‐circuit current density (J_sc) of 22.1 mA cm^?2 can be achieved. By putting the LDS layer in front of the DSSC (transmissive mode), more significant loss channels are observed, and hence a lower overall efficiency than the R‐LDS configuration.     

Highly Catalytic Carbon Nanotube/Pt Nanohybrid‐Based Transparent Counter Electrode for Efficient Dye‐Sensitized Solar Cells

Low‐cost transparent counter electrodes (CEs) for efficient dye‐sensitized solar cells (DSSCs) are prepared by using nanohybrids of carbon nanotube (CNT)‐supported platinum nanoparticles as highly active catalysts. The nanohybrids, synthesized by an ionic‐liquid‐assisted sonochemical method, are directly deposited on either rigid glass or flexible plastic substrates by a facile electrospray method for operation as CEs. Their electrochemical performances are examined by cyclic voltammetry, current density–voltage characteristics, and electrochemical impedance spectroscopy (EIS) measurements. The CNT/Pt hybrid films exhibit high electrocatalytic activity for I^?/I₃^? with a weak dependence on film thickness. A transparent CNT/Pt hybrid CE film about 100 nm thick with a transparency of about 70 % (at 550 nm) can result in a high power conversion efficiency (η) of over 8.5 %, which is comparable to that of pyrolysis platinum‐based DSSCs, but lower cost. Furthermore, DSSC based on flexible CNT/Pt hybrid CE using indium‐doped tin oxide‐coated polyethylene terephthalate as the substrate also exhibits η=8.43 % with J_sc=16.85 mA cm^?2, V_oc=780 mV, and FF=0.64, and this shows great potential in developing highly efficient flexible DSSCs.     

Molecular design of organic dyes with diketopyrrolopyrrole for dye‐sensitized solar cell: A theoretical approach

Three designed metal‐free dyes based on 3‐(10‐butyl‐8‐(methylthio)‐10H‐phenothiazin‐3‐yl)‐2‐cyanoacrylic acid (V5) are investigated by density functional theory (DFT) and time‐dependent DFT to improve the efficiency of V5‐based solar cell devices. We have studied the geometrical structures, excitations, electronic structures, and conduction band shift caused by dye adsorption. The results indicate that the designed dyes have several merits compared with V5 including: (i) smaller energy band gaps and the LUMO closer to conduction band of TiO₂; (ii) wider absorption spectra and higher oscillator strength; (iii) larger dipole moment that lead to higher V_oc value. Our work suggests that the modification of π‐bridge with diketopyrrolopyrrole unit is very effective for designing novel metal‐free dyes with improved performance for dye‐sensitized solar cells (DSSCs). These findings are expected to provide a bright way to design new efficient metal‐free organic DSSCs. © 2014 Wiley Periodicals, Inc.     

A 2D Metal‐Organic Framework Based on 9‐(Pyridin‐4‐yl)‐9H‐carbazole‐3,6‐dicarboxylic Acid: Synthesis,Structure and Properties

A metal‐organic framework (MOF ) formulated as [Cd₂(μ₃‐L)₂(DMF )₄]•H₂O ( CdL ) [H₂L =9‐(pyridin‐4‐yl)‐ 9H ‐carbazole‐3,6‐dicarboxylic acid, DMF =N ,N ‐dimethylformamide] was synthesized under solvothermal condition. Crystal structural analysis reveals that CdL features the layered 2D framework with L^{2 −} ligands as 3‐connected nodes. The compound CdL emits blue‐violet light with the narrow emission peak and the emission maximum at 414 nm upon excitation at the maximum excitation wavelength of 340 nm. The compound CdL has a similar emission spectrum curve to the free H₂L ligand that indicates the emission of compound CdL should be originated from the coordinated L^{2 −} ligands.     

Kinetic study and UV–Vis spectra of 1:2 complexation of free base para‐substituted meso‐tetraphenylporphyrins with trimethylsilyl chloride

The UV–Vis spectra for 1:2 complexation of four different para‐substituted meso‐tetraphenylporphyrin (H₂t(4‐X)pp) and meso‐tetraphenylporphyrins (H₂tpp) with trimethylsilyl chloride (TMSC) displayed large and different redshifts (28–32.4 nm) of Soret and (15–41.7 nm) Q_(0‐0) bands, whereas 1:2 complexation of the less flexible tetramesitylporphyrin (H₂tmp) with TMSC led to rather small redshift (24.8 nm) of the Soret band and blueshift (−7.4 nm) of the Q_(0‐0) band. The varying spectral behavior for the porphyrins complexation seems to essentially reflect the different extent of π‐interactions between the meso‐aryl groups and the presumably saddled porphyrin macrocycle, through their relative coplanarity. The observed order of the rate constants for the complexation of various para‐substituted porphyrins, H₂t(4‐OCH₃)pp (9.27 ± 0.03) × 10⁻³ > H₂t(4‐CH₃)pp (6.68 ± 0.05) × 10⁻³ > H₂tpp (3.2 ± 0.05) × 10⁻³ > H₂t(4‐Cl)pp (8.36 ± 0.06) × 10⁻⁴, clearly demonstrated a higher reaction rate for the porphyrins containing para‐substituents with stronger electron donor ability. The calculated order for porphyrins (0.9 ± 0.1) and for TMSC (1.0 ± 0.1) suggests rate = K[Por][TMSC] for the complexation. Attempts were made to explain the absence of spectral evidence for the presence of an intermediate 1:1 (TMSC) Por adduct in terms of its high reactivity and/or relative instability. © 2007 Wiley Periodicals, Inc. 39: 231–235, 2007     

Photocurrent Enhancement of Dye‐Sensitized Solar Cells owing to Increased Dye‐Adsorption onto Silicon‐Nanoparticle‐Coated Titanium‐Dioxide Films

The inverse‐micellar preparation of Si nanoparticles (Nps) was improved by utilizing sodium naphthalide. The Si Nps were subsequently functionalized with 4‐vinylbenzoic acid for their attachment onto TiO₂ films of dye‐sensitized solar cells (DSSCs). The average diameter of the COOH‐functionalized Si (Si? COOH) Nps was 4.6(±1.7) nm. Depth profiling by secondary‐ion mass spectrometry revealed that the Si Nps were uniformly attached onto the TiO₂ films. The number of Ru^II dye molecules adsorbed onto a TiO₂ film that was treated with the Si? COOH Nps was 42 % higher than that on the untreated TiO₂ film. As a result, DSSCs that incorporated the Si? COOH Nps exhibited higher short‐circuit photocurrent density and an overall energy‐conversion efficiency than the untreated DSSCs by 22 % and 27 %, respectively. This enhanced performance, mostly owing to the intramolecular charge‐transfer to TiO₂ from the dye molecules that were anchored to the Si? COOH Nps, was confirmed by comparing the performance with two different Ru^II–bipyridine dyes (N719 and N749).     

A Novel Coordination Polymer, [Ag4^1 （bpdc）（H2bpdc）（Hbpdc）2]n （bpdc = 2,2＇-bipyridyl-3,3＇-dicarboxylate）： Coordination Models of bpdc Ligands

A novel coordination polymer, [Ag₄ppdc)(H₂bpdc)(Hbpdc)₂] (bpdc = 2,2′‐bipyridyl‐3,3′‐dicarboxylate), was hydrothermally synthesized at 403 K and structurally characterized by single crystal X‐ray diffraction analysis. The compound crystalizes in the monoclinic space group C2/c with a=1.9516(4) nm, b=1.9503(4) nm. c=1.2566(3) nm, and β=112.48(3)°. In the two‐dimensional crystal structure, Ag^I center is coordinated, in a scarce coordination environment, double‐capped tetrahedron, by one bpdc ligand to form N‐Ag‐N chelate bond via two pyridyl N atoms, and other two bpdc ligands to form two O‐Ag‐O chelate bonds, respectively, via two carboxyl O atoms. The bpdc ligands are present in one non‐protonated form, bpdc, and two protonated forms, Hbpdc and H2bpdc, which all act as μ3‐ligand in a hexadentate fashion (N, N′; O, O′; O, O′) to coordinate with three Ag centers, respectively, through the three chelate bonds. This coordinated fashion of bpdc ligand is first found in the title compound. W‐Us‐NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 3.1 eV.     

One‐Dimensional,Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe₂, R=Br; 2 Zn: E=NMe₂, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]_∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and ¹H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies.     

Heterocyclic tautomerism: reassignment of two crystal structures of 2‐amino‐1,3‐thiazolidin‐4‐one derivatives

The structures of 5‐(2‐hydroxyethyl)‐2‐[(pyridin‐2‐yl)amino]‐1,3‐thiazolidin‐4‐one, C₁₀H₁₁N₃O₂S, (I), and ethyl 4‐[(4‐oxo‐1,3‐thiazolidin‐2‐yl)amino]benzoate, C₁₂H₁₂N₂O₃S, (II), which are identical to the entries with refcodes GACXOZ [Váňa et al. (2009). J. Heterocycl. Chem. 46 , 635–639] and HEGLUC [Behbehani & Ibrahim (2012). Molecules, 17 , 6362–6385], respectively, in the Cambridge Structural Database [Allen (2002). Acta Cryst. B 58 , 380–388], have been redetermined at 130 K. This structural study shows that both investigated compounds exist in their crystal structures as the tautomer with the carbonyl–imine group in the five‐membered heterocyclic ring and an exocyclic amine N atom, rather than the previously reported tautomer with a secondary amide group and an exocyclic imine N atom. The physicochemical and spectroscopic data of the two investigated compounds are the same as those of GACXOZ and HEGLUC, respectively. In the thiazolidin‐4‐one system of (I), the S and chiral C atoms, along with the hydroxyethyl group, are disordered. The thiazolidin‐4‐one fragment takes up two alternative locations in the crystal structure, which allows the molecule to adopt R and S configurations. The occupancy factors of the disordered atoms are 0.883 (2) (for the R configuration) and 0.117 (2) (for the S configuration). In (I), the main factor that determines the crystal packing is a system of hydrogen bonds, involving both strong N—H...N and O—H...O and weak C—H...O hydrogen bonds, linking the molecules into a three‐dimensional hydrogen‐bond network. On the other hand, in (II), the molecules are linked via N—H...O hydrogen bonds into chains.     

DFT Calculations,Spectroscopic Studies,Biological Activity and Non Linear Optical Properties (NLO) of Novel Ternary Cu(II)‐Chelates Derived from 5‐Acetyl‐4‐hydroxy‐2H‐1,3‐thiazinedione

New ternary Cu(II)‐chelates with the general formula [ML L′(H₂O)_x] (NO₃)_y x (H₂O), x = 0–2 and y = 0–1, (L) = 5‐acetyl‐4‐hydroxy‐2H‐1,3‐thiazine‐2,6(3H)‐dione with in the presence of a secondary ligand (L′) [N,O‐donor; 8 hydroxyquinoline or N,N‐donor; 1,10‐phenanthroline and diethethylendiamine]. Characterization of the synthesized complexes was established based on elemental analysis, molar conductance, magnetic susceptibility measurements, spectral (infrared, electronic, mass, ¹H‐NMR and ESR) as well as thermal gravimetric analysis (TGA). The complexes exhibited octahedral and square planer geometry. The antimicrobial activity for the studied complexes was tested for different kind of organisms. The geometrical and non‐linear optical parameters of the studied complexes 1–3 are investigated theoretically at the B3LYP/GENECP level of theory. The optimized geometries of the studied complexes are non‐planner as indicated from the dihedral angles. The natural charge population (core, valence and Rydberg), exact electronic configuration, total Lewis, and total non‐Lewis is computed and discussed in terms of natural bond orbitals (NBO) analysis. The calculated E_HOMO and E_LUMO energies at the same level of theory of the studied complexes were used to calculate the global properties; hardness (η), global softness (S), electrophilicity (ω) and electronegativity (χ). The total dipole moment (μ_tot), total and anisotropy of polarizability (? α ?), (Δα) and first hyperpolarizability (? β ?) values were calculated and compared with urea as a reference compound. From the values of the computed first hyperpolarizability (? β ?), the ligand and the studied complexes show promising optical properties.     

Dye‐sensitized solar cells based on zinc(II) phthalocyanines bearing 3‐pyridin‐3‐ylpropoxy anchoring groups

In this study, nonperipherally tetra‐substituted ( 2 ), peripherally tetra‐substituted ( 3 ), and peripherally octa‐substituted ( 4 ) zinc(II) phthalocyanines were synthesized as sensitizers for dye‐sensitized solar cells (DSSCs) in which 3‐pyridin‐3‐ylpropoxy substituent acts as anchoring unit to bind TiO₂ surface. The optical results indicated that there is an interaction between the dyes and the TiO₂ surface. The photovoltaic performances of the DSSCs based on these dyes were found to depend on both the position and number of the substituents. Despite the more red‐shifted absorption, the DSSC based on 2 showed the conversion efficiency of 0.68%, which is lower than 1.36% and 0.92% for 3 and 4 , respectively, under one sun (AM 1.5G). The vertical orientation of the dye on TiO₂ surface could be the main reason for the higher photovoltaic performance of complex 3 , which is beneficial for not only injecting the electrons into the conduction band of TiO₂ but also reducing the charge recombination. Overall, these results demonstrate that the peripherally tetra‐substituted 3‐pyridin‐3‐ylpropoxy zinc(II) phthalocyanine complex ( 3 ) as a sensitizer can more efficiently utilize the photons in the red/near‐infrared region with respect to the other complexes studied.     

Water Soluble Gold(I)‐diacetyl‐1,3,5‐triaza‐7‐phosphaadamantane‐arylazoimidazole Complexes: Synthesis and Spectroscopic Study

Reaction of [Au(DAPTA)(Cl)] with RaaiR’ in CH2Cl2 medium following ligand addition leads to [Au(DAPTA)(RaaiR’)](Cl) [DAPTA＝diacetyl-1,3,5-triaza-7-phosphaadamantane, RaaiR’＝p-R-C6H4-N＝N- C3H2-NN-1-R’, (1—3), abbreviated as N,N’-chelator, where N(imidazole) and N(azo) represent N and N’, respectively; R＝H (a), Me (b), Cl (c) and R’＝Me (1), CH2CH3 (2), CH2Ph (3)]. The 1H NMR spectral measurements in D2O suggest methylene, CH2, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C NMR spectrum in D2O suggest the molecular skeleton. The 1H-1H COSY spectrum in D2O as well as contour peaks in the 1H-13C HMQC spectrum in D2O assign the solution structure.     

(1R,2S)‐2‐[N‐Methyl‐N‐(4‐toluene­sulfonyl)amino]‐1‐phenylpropan‐1‐ol

In the title compound, C₁₇H₂₁NO₃S, the S atom is in a distorted tetrahedral geometry and the N atom exhibits sp² character. The antiperiplanar conformation is observed for the N and hydroxyl‐O atoms and the torsion angle around the N—C linkage is ?136.3 (2)°. The mol­ecules are linked by O—H?O intermolecular hydrogen bonds to form an infinite one‐dimensional chains along the c axis.     

Structure and electrospray mass spectrometry studies on dithiacyclooctan-3-ol-containing palladium (II) complex of trans -[Pd(dtco-3-OH)_2](ClO_4)_2·2DMSO

The structure of trans-[Pd(dtco-3-OH)2] (ClO4)2·2DMSO, in which dtco-3-OH is dithiacyclooctan-3-ol and DMSO is dimethyl sulfoxide, was determined by X-ray crystallographic analysis. The crystal data: space group pi, a = 0.7077(2) nm, b = 1.0788(1) nm, c = 1.1111(1) nm, α=67.710(8)°, β = 73. 59(2)°, γ = 85. 39(2)°,R1 = 0 . 0368 and Rw = 0.0998. The palladium (II) is coordinated by four sulfur atoms with a regular square planar configuration. The Pd-S distances are 0.2314(1) and 0.2317(1) nm, respectively. Both dtco-3-OH ligands are in the boat-chair configuration and two hydroxyl groups are on the opposite sites of the PdS4 coordination plane and are towards Pd(II). The Pd-O distance is 0. 285 nm, indicating a weak interaction between them. A typical hydrogen bond between the hydroxyl group of dtco-3-OH ligand and DMSO was observed in the crystal structure. An aqueous solution prepared with the crystals of the complex was used for the investigation of electrospray mass spectrometry ( ESMS ). Besid     

Hydrogen bonding in polyamino‐polyalcohols: a monohydrated cocrystal of 1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol iodide and 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol

In the title monohydrated cocrystal, namely 1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol iodide–1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol–water (1/1/1), C₆H₁₆N₃O₃⁺·I⁻·C₆H₁₅N₃O₃·H₂O, the neutral 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol (taci) molecule and the monoprotonated 1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol cation (Htaci⁺) both adopt a chair conformation, with the three O atoms in axial and the three N atoms in equatorial positions. The cation, but not the neutral taci unit, exhibits intramolecular O—H...O hydrogen bonding. The entire structure is stabilized by a complex three‐dimensional network of intermolecular hydrogen bonds. The neutral taci entities and the Htaci⁺ cations are each aligned into chains along [001]. In these chains, two O—H...N interactions generate a ten‐membered ring as the predominant structural motif. The rings consist of vicinal 2‐amino‐1‐hydroxyethylene units of neighbouring molecules, which are paired via centres of inversion. The chains are interconnected into undulating layers parallel to the ac plane, and the layers are further held together by O—H...N hydrogen bonds and additional interactions with the iodide counter‐anions and solvent water molecules.     

Crystallographic study of self‐organization in the solid state including quasi‐aromatic pseudo‐ring stacking interactions in 1‐benzoyl‐3‐(3,4‐dimethoxyphenyl)thiourea and 1‐benzoyl‐3‐(2‐hydroxypropyl)thiourea

1‐Benzoylthioureas contain both carbonyl and thiocarbonyl functional groups and are of interest for their biological activity, metal coordination ability and involvement in hydrogen‐bond formation. Two novel 1‐benzoylthiourea derivatives, namely 1‐benzoyl‐3‐(3,4‐dimethoxyphenyl)thiourea, C₁₆H₁₆N₂O₃S, (I), and 1‐benzoyl‐3‐(2‐hydroxypropyl)thiourea, C₁₁H₁₄N₂O₂S, (II), have been synthesized and characterized. Compound (I) crystallizes in the space group P , while (II) crystallizes in the space group P 2₁/c . In both structures, intramolecular N—H…O hydrogen bonding is present. The resulting six‐membered pseudo‐rings are quasi‐aromatic and, in each case, interact with phenyl rings via stacking‐type interactions. C—H…O, C—H…S and C—H…π interactions are also present. In (I), there is one molecule in the asymmetric unit. Pairs of molecules are connected via two intermolecular N—H…S hydrogen bonds, forming centrosymmetric dimers. In (II), there are two symmetry‐independent molecules that differ mainly in the relative orientations of the phenyl rings with respect to the thiourea cores. Additional strong hydrogen‐bond donor and acceptor –OH groups participate in the formation of intermolecular N—H…O and O—H…S hydrogen bonds that join molecules into chains extending in the [001] direction.     

Synthesis and properties of cationic polyelectrolyte with regioregular polyalkylthiophene backbone and ionic‐liquid like side groups

High‐regioregular poly{3‐[6‐(1‐methylimidazolium‐3‐yl)hexyl]thiophene‐2,5‐diyl bromide}, PMHT‐Br, has been prepared by reaction of high‐regioregular (above 92%) poly[3‐(6‐bromohexyl)thiophene‐2,5‐diyl] with 1‐methylimidazole. PMHT‐Br is soluble in water and water miscible solvents such as methanol, DMSO and shows solvatochromism; λ_max (nm): 423 (H₂O); 435 (MeOH); 452 (DMSO). Increased absorption band broadening observed for aqueous solution as well as NMR spectra in D₂O suggests a micelle‐like structure of PMHT‐Br molecules in these solutions: poly(3‐hexylthiophene) core and 1‐methylimidazolium bromide shell. Despite the disturbing effect of ionic groups, the solid‐state PMHT‐Br shows absorption maximum at 520 nm, the band edge at 660 nm (ca. 1.9 eV), and fluorescence emission with maximum at 635 nm, in a good agreement with the polymer regioregularity. Fluorescence emission maxima: λ_em (nm): 598 (H₂O); 562 (MeOH); 574 (DMSO), occur in a vicinity of corresponding adsorption band edges. Plot of electrical conductivity of PMHT‐Br (measured under the dynamic vacuum conditions, 5 × 10^?5 Pa) versus 1/T shows a break at about 70 °C same as the temperature dependence of λ_max of the solid PMHT‐Br. These breaks indicate an increase in the mobility of polymer segments and ions within PMHT‐Br; however, a thermal analysis did not provide solid evidence for it. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3073–3081, 2010     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。     

Supramolecular hydrogen‐bonding patterns in two cocrystals of the N(7)–H tautomeric form of N6‐benzoyladenine: N6‐benzoyladenine–3‐hydroxypyridinium‐2‐carboxylate (1/1) and N6‐benzoyladenine–DL‐tartaric acid (1/1)

Two novel cocrystals of the N(7)—H tautomeric form of N⁶‐benzoyladenine (BA), namely N⁶‐benzoyladenine–3‐hydroxypyridinium‐2‐carboxylate (3HPA) (1/1), C₁₂H₉N₅O·C₆H₅NO₃, (I), and N⁶‐benzoyladenine–DL‐tartaric acid (TA) (1/1), C₁₂H₉N₅O·C₄H₆O₆, (II), are reported. In both cocrystals, the N⁶‐benzoyladenine molecule exists as the N(7)—H tautomer, and this tautomeric form is stabilized by intramolecular N—H...O hydrogen bonding between the benzoyl C=O group and the N(7)—H hydrogen on the Hoogsteen site of the purine ring, forming an S(7) motif. The dihedral angle between the adenine and phenyl planes is 0.94 (8)° in (I) and 9.77 (8)° in (II). In (I), the Watson–Crick face of BA (N6—H and N1; purine numbering) interacts with the carboxylate and phenol groups of 3HPA through N—H...O and O—H...N hydrogen bonds, generating a ring‐motif heterosynthon [graph set R₂²(6)]. However, in (II), the Hoogsteen face of BA (benzoyl O atom and N7; purine numbering) interacts with TA (hydroxy and carbonyl O atoms) through N—H...O and O—H...O hydrogen bonds, generating a different heterosynthon [graph set R₂²(4)]. Both crystal structures are further stabilized by π–π stacking interactions.