Synthesis and Crystal Structure of Two Cyano Bridged dimeric 4f-3d Complexes

Two cyano bridged dimeric 4f 3d complexes [Nd(DMF) 4(H 2O) 3Co(CN) 6]·H 2O (A) and [Sm(pyr) 4(H 2O) 3Cr(CN) 6]·2H 2O (B) (DMF=N,N dimethylformamide, pyr=2 pyrrolidone) were prepared and structurally characterized. Single crystal X ray diffraction analysis revealed that the complexes contain cyano bridged 3 and [Ln(L) 4(H 2O) 3] 3+ groups. The Ln 3+ is eight coordinate, and is coordinated by seven oxygen atoms of three water molecules and four organic ligands (DMF or pyr). Each terminal CN ligand of the 3- entity is hydrogen bonded to some oxygen atoms of the coordinated water molecules yielding a hydrogen bonded three dimensional network. Crystal data for A: monoclinic, space group P 2(1)/ n , a = 1.7525(4) nm, b =0.8879(2) nm, c =1.9876(4) nm, β =95.92(3)°, V =3.0763(12) nm 3, Z =4, D c= 1.563 mg·m -3 . Complex B crystallizes in the P 1 space group, with lattice parameters of a =1.22720(4) nm, b =1.45550(8) nm, c =0.91310(4) nm, α =92.5869(17)°, β = 90.9569(12)°, γ =89.822(3)°, V =1.62908(13) nm 3, Z =2, D c=1.608 mg·m -3 .

A Facile Synthesis of 2-Amino-5-Cyano-4, 6-Disubstitutedpyrimidines under MWI

Microwave Assisted Organic Synthesis (MAOS) is energy efficient and effective tool to speed up the synthesis for drug discovery process. In the present study we report a novel protocol for the rapid, high throughput synthesis of mononuclear 2-amino-5-cyano-4,6-disubstituted pyrimidines, adaptable to parallel synthesis for compound libraries. The overall reaction time in hrs has been reduced to 25 - 50 minutes with improved yields.

Construction of efficient active sites through cyano‐modified graphitic carbon nitride for photocatalytic CO_(2) reduction

The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits moderate photocatalytic activity due to insufficient active sites.In this study,cyano‐modified porous g‐C_(3)N_(4)nanosheets(MCN‐0.5)were synthesized through molecular self‐assembly and alkali‐assisted strategies.The cyano group acted as the active site of the photocatalytic reaction,because the good electron‐withdrawing property of the cyano group promoted carrier separation.Benefiting from the effect of the active sites,MCN‐0.5 exhibited significantly enhanced photocatalytic activity for CO2 reduction under visible light irradiation.Notably,the photocatalytic activity of MCN‐0.5 was significantly reduced when the cyano groups were removed by hydrochloric acid(HCl)treatment,further verifying the role of cyano groups as active sites.The photoreduction of Pt nanoparticles provided an intuitive indication that the introduction of cyano groups provided more active sites for the photocatalytic reaction.Furthermore,the controlled experiments showed that g‐C_(3)N_(4)grafted with cyano groups using melamine as the precursor exhibited enhanced photocatalytic activity,which proved the versatility of the strategy for enhancing the activity of g‐C_(3)N_(4)via cyano group modification.In situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations were used to investigate the mechanism of enhanced photocatalytic activity for CO2 reduction by cyano‐modified g‐C_(3)N_(4).This work provides a promising route for promoting efficient solar energy conversion by designing active sites in photocatalysts.

A Three-dimensional Porous Metal-organic Framework Based on Cyano Unit and 1,4-Bis(1,2,4-triazol-1-yl)butane(btb):{[Cu_8(btb)_2(CN)_8].3H_2O}_n

The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.

Regioisomeric Polymer Semiconductors Based on Cyano-Functionalized Dialkoxybithiophenes:Structure-Property Relationship and Photovoltaic Performance

Cyano substitution is vital to the molecular design of polymer semiconductors toward highly efficient organic solar cells.However,how regioselectivity impacts relevant optoelectronic properties in cyano-substituted bithiophene systems remain poorly understood.Three regioisomeric cyano-functionalized dialkoxybithiophenes BT_(HH),BT_(HT),and BT_(TT) with headto-head,head-to-tail,and tail-to-tail linkage,respectively,were synthesized and characterized in this work.The resulting polymer semiconductors(PBDTBTs)based on these building blocks were prepared accordingly.The regiochemistry and property relationships of PBDTBTs were investigated in detail.The BTHH moiety has a higher torsional barrier than the analogs BT_(HT) and BT_(TT),and the regiochemistry of dialkoxybithiophenes leads to fine modulation in the optoelectronic properties of these polymers,such as optical absorption,band gap,and energy levels of frontier molecular orbitals.Organic field-effect transistors based on PBDTBT_(HH) had higher hole mobility(4.4×10^(-3) cm^(2)/(V·s))than those(ca.10^(-4) cm^(2)/(V·s))of the other two polymer analogs.Significantly different short-circuit current densities and fill factors were obtained in polymer solar cells using PBDTBTs as the electron donors.Such difference was probed in greater detail by performing space-charge-limited current mobility,thin-film morphology,and transient photocurrent/photovoltage characterizations.The findings highlight that the BTHH unit is a promising building block for the construction of polymer donors for highperformance organic photovoltaic cells.

A bilateral cyano molecule serving as an effective additive enables high-efficiency and stable perovskite solar cells

The existence of defects in perovskite films is a major obstacle that prevents perovskite solar cells (PSCs) from high efficiency and long-term stability. A variety of additives have been introduced into perovskite films for reducing the number of defects. Lewis base-based additive engineering has been considered as an effective way to eliminate defects, especially the defects caused by the uncoordinated Pb^(2+). In this work, for the first time, a bilateral cyano molecule (succinonitrile, SN) which is a commonly used plasticizer in solid electrolyte of solid-state lithium batteries was selected as an additive to modify organic–inorganic hybrid perovskite films in PSCs. SN is featured with two cyano groups (–C≡N) distributing at both terminals of the carbon chain, providing two cross-linking points to interact with perovskites crystals via coordinating with uncoordinated Pb2+ and forming hydrogen bonds with –NH2 groups in perovskite. It was found that the addition of SN into perovskite precursor solution could effectively reduce defects, particularly inhibit the appearance of Pb0 and thus suppress trap-assisted nonradiative charge carrier recombination. As a result, the efficiency of CH_(3)NH_(3)PbI_(3)(Cl) (MAPbI_(3)(Cl))-based PSCs was improved from 18.4% to 20._(3)% with enhanced long-term stability at N2 and humid air atmosphere. This work provides a facile and effective strategy to enhance the PCE and stability of PSCs simultaneously, facilitating the commercialization of PSCs.

Microwave promoted one-pot synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins

A facile procedure for the synthesis of 3-（2′-amino-3′-cyano-4′-arylpyrid-6′-yl） coumarins are being reported starting from 3- acetylcoumarin, aromatic aldehydes and malononitrile. The reactions were carried out on microwave irradiation in good yield with short time and easy work-up. The structures of all the compounds have been confirmed on the basis of their analytical, IR, ^1H NMR, and mass spectral data.

Adsorption equilibrium of citric acid from supercritical carbon dioxide/ethanol on cyano column

Supercritical adsorption equilibrium has a significant role in defining supercritical adsorption behavior. In this paper, the adsorption equilibrium of citric acid from supercritical CO2/ethanol on a cyano column was systematically investigated with the elution by characteristic point method. Equilibrium loading was obtained at 313.15 K and 321.15 K with supercritical CO2/ethanol densities varying from 0.7068 g·cm-3to 0.8019 g·cm-3. The experimental results showed that the adsorption capacity of citric acid decreased with increasing temperature and increasing density of the supercritical CO2/ethanol mobile phase. The adsorption equilibrium data were fitted well by the Quadratic Hill isotherm model and the isotherms showed anti-Langmuir behavior. The monolayer saturation adsorption capacity of citric acid is in the range of 44.54 mg·cm-3to 64.66 mg·cm-3with an average value of 56.86 mg·cm-3.

CATALYTIC SYNTHESIS OF α-CYANO-α,β-UNSATURATED SULPHONES IN THE PRESENCE OF ORGANOTELLURIUM OXIDE

Using bis(p-methoxyphenyl)telluroxide(BMPTO)as the catalyst, phenylsulphonyl acetonitrile condensed easily with aromatic aldehydes at room temperature to give -cyano- ,β-unsaturated sulphones in high yields.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex K_3(TMS)_2(H_2O)_2Cr(CN)_6[TMS = Tetramethylene Sulfone]

The cyano-bridged bimetallic complex K3(TMS)2(H2O)2Cr(CN)6 with three- dimensional microporous structure was synthesized and characterized. The title complex (C14H20CrK3N, Mr = 601.78) crystallizes in monoclinic, space group C2/c with a = 14.357(4), b = 9.331(3), c = 19.180(6) ?, β = 96.754(5)o, V = 2551.6(13) ?3, Z = 4, Dc = 1.567 g/m3, μ(MoKα) = 1.141 mm-1, F(000) = 1228, the final R = 0.0440 and wR = 0.0990 for 1760 observed reflections (I > 2σ(I)). In the crystal, two [Cr(CN) ]3- units, four K+ ions and two oxygen atoms of two 6 TMS molecules are linked to form a sixteen-membered ring and an extended three-dimensional structure.

Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ) Complex [La(DMSO)_5(H_2O)](μ-CN)_2[Fe(CN)_4]·H_2O

ABSTRACT A new lanthanumm-ironm complex [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4]·H2O 1 （DMSO = dimethylsulfoxide） has been prepared by a facile approach, ball-milling method, and characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 9.7125（3）, b = 21.5336（7）, c = 14.3804（5）A, β = 93.242（3）°, C16H34FeLaN60O7S5, Mr= 777.55, V = 3002.8（2）A^3, Z = 4, Dc = 1.720 g/cm^3, S = 1.053, μ（MoKα） = 2.278 mm^-1, F（000） = 1564, R = 0.0490 and ωR = 0.1270. The crystal structure analysis of 1 reveals a slightly distorted squareantiprism eighffold-coordinated La（Ⅲ） ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4] species are held together via hydrogen bonds to form a three-dimensional framework.

A novel synthesis of 5-aryl-3-cyano-2-pyridones by using vinamidinium salts

A variety of vinamidinium salts were condensated with cyanoacetamide in refluxing methanol that contained sodium methoxide to produce 5-aryl-3-cyano-2-pyridones in good yield. Simple experimental conditions were used to prepare ten different 5-aryl-3- cyano-2-pyridones, four of which are new compounds.C 2009 Song Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex[La(betaine)_2(H_2O)_6Fe(CN)_6]·2H_2O

The title complex [La(betaine)2(H2O)6Fe(CN)6]?2H2O (betaine = (CH3)3NCH2CO2) has been synthesized and characterized by X-ray single-crystal structure analysis. The crystal crystallizes in monoclinic, space group P21/n with a = 15.793(5), b = 8.927(3), c = 22.257(7) ?, β = 110.147(5)o, C16H38FeLaN8O12, Mr = 729.31, Z = 4, V = 2946.0(15) ?3, Dc = 1.640 g/m3, μ(MoKα) = 1.988 mm-1, F(000) =1476, R = 0.0388 and wR = 0.0827 for 4237 observed reflections (I > 2σ(I)). The La3+ ion is nine-coordinated by one cyano nitrogen atom and eight oxygen atoms of two betaine and six water molecules. Each complex molecule is connected to form a 3D network structure by some O–H…O and O–H…N hydrogen bonds.

Synthesis and Structural Characterization of a Cyano-bridged Dinuclear Neodymium(III)-iron(III) Complex [Nd(DMSO)_5(H_2O)_2](μ-CN)[Fe(CN)_5]

A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8.859(4), b = 13.684(5), c = 12.290(4) ?, ?= 91.85(2)o, C16H34FeN6NdO7S5, Mr= 782.88, V = 1489(1) ?3, Z = 2, Dc = 1.746 g/cm3, S = 0.906, μ(MoKa) = 2.606 mm-1, F(000) = 788, R = 0.0646 and wR = 0.1654. The slightly distorted square-antiprism eightfold-coordinated Nd(III) and approximately oriented octahedrally sixfold- coordinated Fe(III) are linked by a cyano-bridge group to construct a dinuclear compound. The [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] species are held together via hydrogen bonds to form a three-dimensional framework.

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {(NH_4)_2[Cd(H_2O)Fe(CN)_6]}_n:Synthesis and Crystal Structure

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ln(DMSO)_2(H_2O)(μ-CN)_4Fe(CN)_2] (Ln = Ce and Eu, DMSO = Dimethylsulfoxide) with Layered Structure

Two new bimetallic cyano-bridged complexes [Ln（DMSO）2（H2O）（μ-CN）4Fe（CN）2] （Ln = Ce 1, Eu 2） have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1： C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852（4）, b = 10.729（5）, c = 11.181（5）A,β = 96.992（8）°, V = 935.0（7） A^3, Z = 2, Dc = 1.870 g/cm^3,/1 = 3.421 mm^-1, F（000） = 512, R = 0.0363 and wR = 0.0971; and those for 2： C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P21n, a = 7.739（5）, b = 10.668（7）, c = 11.008（7） A,β = 96.943（3）°, V = 902.1（11） A^3, Z = 2, Dc = 1.981 g/cm^3,/1 = 4.499 mm^-1, F（000） = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe（Ⅲ） ion is in a nearly regular octahedral environment. The title complexes can be described as two- dimensional （2-D） stair-like structures, which are further connected by hydrogen bonds to form three-dimensional （3-D） frameworks.

Synthesis of 1,2:4,5-di-O-Isopropylidene-3-C-Cyano-β-D-ribo-hex-2-ulo Pyranose by Phase Transition Catalysis

Introduction The cyano branched carbohydrates are useful, versatil intermediaries for the synthesis of branched sugars having biological activity in nature. Owing to the good yield, mild reaction conditions and high stereospecificity, the phase transition catalysis(PTC)method has been widely used to the syntheses of C-

Synthesis and Crystal Structure of 1-Methylsulfinyl-1-methylthio-2-cyano-2-phenylethylene

The crystal of the title compound (C_ 11H_ 11NOS_2, M_r =237.33) has been prepared and determined by X-ray single crystal diffraction. The crystal is monoclinic, space group P2_1/c with parameters : a=5.484 (1), b=7.793(2), c=28.295(6), β=90.277(4)°, V=1209.2(5)3, Z=4, D_c=1.034 g/cm3, μ(MoKα)= 0.413 mm -1, F(000)=496, the final R=0.0390 and wR=0.1051 for 1500 observed reflections with I>2σ(I). The X-ray analysis result shows that the orientation of methylsulfinyl and phenyl is the cis and confirms the E-stereochemistry of the title compound.

Nickel-catalyzed arylcyanation of alkenes via cyano group translocation:access to 1,n-dinitriles or 4-amino nitriles

Herein,a nickel-catalyzed arylcyanation of unactivated alkenes via cyano group translocation with aryl boronic acids has been developed.These transformations provided a robust approach to constructing structurally diverse 1,n-dinitriles or 4-amino nitriles from easily prepared and commercially available starting materials.The cyano group translocation was achieved,involving the addition into the intramolecular C–N triple bond followed by the retro-Thorpe reaction.Mechanistic studies revealed that high temperature and CsHCO_(3) as the base were crucial for the cyano group translocation.

Surface doping effect on the optoelectronic performance of 2D organic crystals based on cyano-substituted perylene diimides

Compared to organic thin films,organic single crystals offer significant potential in organic phototransistors(OPTs)due to their enhanced charge transport,large surface area,and defect-free nature.However,the development of n-type semiconductors has lagged behind p-type semiconductors.To enhance semiconductor device performance,a doping process can be employed,which typically involves the introduction of charged impurities into the crystalline semiconducting material.Its aim is to reduce the Ohmic losses,increase carrier density,improve transport capabilities,and facilitate effective carrier injection,ultimately enhancing the electrical properties of the material.Traditional doping processes,however,often pose a risk of damaging the structure of single crystals.In this study,we have synthesized novel cyanosubstituted chiral perylene diimides,which self-assemble into two-dimensional single crystals that can be used for n-type semiconductor devices.We have employed a surface doping strategy using diethylamine vapor without disrupting the crystal structure.The fabricated devices exhibit significantly higher charge transport properties after doping,achieving a maximum electron mobility of 0.14 cm^(2)V^(-1)s^(-1),representing an improvement of over threefold.Furthermore,the optoelectronic performance of the doped devices has significantly improved,with the external quantum efficiency increased by over 9 times and the significantly improved response time.These results suggest that our surface doping technology is a promising way for enhancing the performance of 2D organic single-crystal OPTs.