Effective Synthesis of N‐Arylformamide from α‐Halo‐N‐arylacetamides

A convenient synthetic method for N‐arylformamide derivatives was successfully developed by reacting α‐iodo‐N‐arylacetamides with formamide. This method was applicable to α‐iodo‐N‐arylacetamide substrates bearing electron‐donating or electron‐withdrawing groups, N‐(benzo[d][1,3]dioxol‐5‐yl)‐2‐iodoacetamide, 2‐iodo‐N‐(pyridin‐2‐yl)acetamide, and 2‐iodo‐N‐(naphthalen‐4‐yl)acetamide to give the corresponding N‐arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation.     

Highly efficient blue organic light-emitting diodes based on 2-(diphenylamino)fluoren-7-ylvinylarene derivatives that bear a tert-butyl group

Blue fluorescent materials with a 2‐(diphenylamino)fluoren‐7‐ylvinylarene emitting unit and tert‐butyl‐based blocking units were synthesized. The photophysical properties of these materials, including UV/Vis absorption, photoluminescent properties, and HOMO–LUMO energy levels, were characterized and rationalized with quantum‐mechanical DFT calculations. The electroluminescent properties of these molecules were examined through the fabrication of multilayer devices with a structure of indium–tin oxide, 4,4′‐bis{N‐[4‐(N,N‐di‐m‐tolylamino)phenyl]‐N‐phenylamino}biphenyl, 4′‐bis[N‐(1‐naphthyl)‐N‐phenylamino]biphenyl, and blue materials doped in 2‐methyl‐9,10‐di(2‐naphthyl)anthracene/tris(8‐quinolinolato)aluminum/LiF/Al. All devices exhibit highly efficient blue electroluminescence with high external quantum efficiency (3.20–7.72 % at 20 mA cm^?2). A deep‐blue device with Commission Internationale de l’Eclairage (CIE) coordinates of (0.15, 0.11) that uses 7‐[2‐(3′,5′‐di‐tert‐butylbiphenyl‐4‐yl)vinyl]‐9,9‐diethyl‐2‐N‐(3,5‐di‐tert‐butylphenyl)‐2,4‐difluorobenzenamino‐9H‐fluorene as a dopant in the emitting layer showed a luminous efficiency and external quantum efficiency of 3.95 cd A^?1 and 4.23 % at 20 mA cm^?2, respectively. Furthermore, a highly efficient sky‐blue device that uses the dopant 7‐{2‐[2‐(3,5‐di‐tert‐butylphenyl)‐9,9′‐spirobifluorene‐7‐yl]vinyl}‐9,9‐diethyl‐2‐N,N‐diphenylamino‐9H‐fluorene exhibited a luminous efficiency and high quantum efficiency of 10.3 cd A^?1 and 7.7 % at 20 mA cm^?2, respectively, with CIE coordinates of (0.15, 0.20).     

Synthesis and reactions of 3‐amino‐2‐methyl‐3H‐[1,2,4]triazolo[5,1‐b]‐quinazolin‐9‐one and 2‐hydrazino‐3‐phenylamino‐3H‐quinazolin‐4‐one

The reaction of 3‐N‐(2‐mercapto‐4‐oxo‐4H‐quinazolin‐3‐yl)acetamide ( 1 ) with hydrazine hydrate yielded 3‐amino‐2‐methyl‐3H‐[1,2,4]triazolo[5,1‐b]quinazolin‐9‐one ( 2 ). The reaction of 2 with o‐chlorobenzaldehyde and 2‐hydroxy‐naphthaldehyde gave the corresponding 3‐arylidene amino derivatives 3 and 4 , respectively. Condensation of 2 with 1‐nitroso‐2‐naphthol afforded the corresponding 3‐(2‐hydroxy‐naphthalen‐1‐yl‐diazenyl)‐2‐methyl‐3H‐[1,2,4]triazolo[5,1‐b]quinazolin‐9‐one ( 5 ), which on subsequent reduction by SnCl₂ and HCl gave the hydrazino derivative 6. Reaction of 2 with phenyl isothiocyanate in refluxing ethanol yielded thiourea derivative 7. Ring closure of 7 subsequently cyclized on refluxing with phencyl bromide, oxalyl dichloride and chloroacetic acid afforded the corresponding thiazolidine derivatives 8, 9 and 10 , respectively. Reaction of 2‐mercapto‐3‐phenylamino‐3H‐quinazolin‐4‐one ( 11 ) with hydrazine hydrate afforded 2‐hydrazino‐3‐phenylamino‐3H‐quinazolin‐4‐one ( 12 ). The reactivity 12 towards carbon disulphide, acetyl acetone and ethyl acetoacetate gave 13, 14 and 15 , respectively. Condensation of 12 with isatin afforded 2‐[N‐(2‐oxo‐1,2‐dihydroindol‐3‐ylidene)hydrazino]‐3‐phenylamino‐3H‐quinazolin‐4‐one ( 16 ). 2‐(4‐Oxo‐3‐phenylamino‐3,4‐dihydroquinazolin‐2‐ylamino)isoindole‐1,3‐dione ( 17 ) was synthesized by the reaction of 12 with phthalic anhydride. All isolated products were confirmed by their ir, ¹H nmr, ¹³C nmr and mass spectra.     

Syntheses and optoelectronic properties of quinoxaline polymers: The effect of donor unit

Tuning the bandgap of electrochromic polymers is one of the important research topics in electrochromism. To understand clearly the effect of donor unit in donor–acceptor–donor‐type polymers, 2,3‐bis(4‐tert‐butylphenyl)‐5,8‐di(thiophen‐2‐yl)quinoxaline and 2,3‐bis(4‐tert‐butylphenyl)‐5‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐ 5‐yl)‐8‐(thiophen‐2‐yl)quinoxaline were synthesized and polymerized potentiodynamically. Their electrochemical and spectroelectrochemical studies were performed, and the results were compared with those of poly(2,3‐bis(4‐tert‐butylphenyl)‐5,8‐bis(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)quinoxaline) (Gunbas et al., Adv Mater 2008, 20, 691–695). A blue shift in the polymer π–π* transitions revealed that the bandgap of such polymers with the same acceptor unit is related to the electron density of donor units. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis,crystal structure and photophysical properties of 1,4‐bis(1,3‐diazaazulen‐2‐yl)benzene: a new π building block

A dimerized 1,3‐diazaazulene derivative, namely 1,4‐bis(1,3‐diazaazulen‐2‐yl)benzene [or 2,2′‐(1,4‐phenylene)bis(1,3‐diazaazulene)], C₂₂H₁₄N₄, (I), has been synthesized successfully through the condensation reaction between 2‐methoxytropone and benzene‐1,4‐dicarboximidamide hydrochloride, and was characterized by ¹H NMR and ¹³C NMR spectroscopies, and ESI–MS. X‐ray diffraction analysis reveals that (I) has a nearly planar structure with good π‐electron delocalization, indicating that it might serve as a π building block. The crystal belongs to the monoclinic system. One‐dimensional chains were formed along the a axis through π–π interactions and adjacent chains are stabilized by C—H…N interactions, forming a three‐dimensional architecture. The solid emission of (I) in the crystalline form exhibited a 170 nm red shift compared with that in the solution state. The observed optical bandgap for (I) is 3.22 eV and a cyclic voltammetry experiment confirmed the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The calculated bandgap for (I) is 3.37 eV, which is very close to the experimental result. In addition, the polarizability and hyperpolarizability of (I) were appraised for its further application in second‐order nonlinear optical materials.     

Synthesis and evaluation of polyacrylamides derived from polycyclic pendant naphthalene,indole, and phenothiazine based chalcone moiety as potent antimicrobial agents

Polycyclic chalcone‐containing polyacrylamides, namely, poly ((N‐(4‐((E)‐3‐(naphthalen‐6‐yl)‐3‐oxoprop‐1‐enyl) phenyl) acrylamide), poly((N‐(4‐((E)‐3‐(1H‐indol‐3‐yl)‐3‐oxoprop‐1‐enyl) phenyl) acrylamide), and poly((N‐(4‐((E)‐3‐oxo‐3‐(10H‐phenothiazin‐8‐yl) prop‐1‐enyl) phenyl) acrylamide), were synthesized by Claisen–Schmidt condensation reaction, followed by ultrasonic irradiation reduction. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance, and ¹³C nuclear magnetic resonance spectroscopic technique. The newly synthesized polymers have been screened for antibacterial and antifungal activities by using resazurin reduction assay method, and the resulting polyacrylamides showed promising activity against various tested bacteria and fungi. Among the polymers, poly((N‐(4‐((E)‐3‐oxo‐3‐(10H‐phenothiazin‐8‐yl) prop‐1‐enyl) phenyl) acrylamide) and poly((N‐(4‐((E)‐3‐(1H‐indol‐3‐yl)‐3‐oxoprop‐1‐enyl) phenyl) acrylamide) exhibited better antifungal and antibacterial activities than poly ((N‐(4‐((E)‐3‐(naphthalen‐6‐yl)‐3‐oxoprop‐1‐enyl) phenyl) acrylamide), whereas all the polymers do not show any sign of antibacterial and antifungal activity against Streptococcus faecalis and Candida glabrata. Copyright © 2016 John Wiley & Sons, Ltd.     

Iron(III) Catecholates for Cellular Imaging and Photocytotoxicity in Red Light

Iron(III) complexes [Fe( L )( L′ )(NO₃)]—in which L is phenyl‐N,N‐bis[(pyridin‐2‐yl)methyl]methanamine ( 1 ), (anthracen‐9‐yl)‐N,N‐bis[(pyridin‐2‐yl)methyl]methanamine ( 2 ), (pyreny‐1‐yl)‐N,N‐bis[(pyridin‐2‐yl)methyl]methanamine ( 3 – 5 ), and L′ is catecholate ( 1 – 3 ), 4‐tert‐butyl catecholate ( 4 ), and 4‐(2‐aminoethyl)‐benzene‐1,2‐diolate ( 5 )—were synthesized and their photocytotoxic properties examined. The five electron‐paramagnetic complexes displayed a Fe^III/Fe^II redox couple near ?0.4 V versus a saturated calomel electrode (SCE) in DMF/0.1 m tetrabutylammonium perchlorate (TBAP). They showed unprecedented photocytotoxicity in red light (600–720 nm) to give IC₅₀≈15 μM in various cell lines by means of apoptosis to generate reactive oxygen species. They were ingested in the nucleus of HeLa and HaCaT cells in 4 h, thereby interacting favorably with calf thymus (ct)‐DNA and photocleaving pUC19 DNA in red light of 785 nm to form hydroxyl radicals.     

二茂铁-噻吩和联噻吩桥连吡啶盐类化合物的合成与电化学性质

设计并合成了3个二取代和三取代的二茂铁-噻吩、二茂铁-联噻吩吡啶盐类化合物： 碘化(E,E)-N-甲基-2,4,6-三{2-[5-(2-二茂铁乙烯基)噻吩-2-基]乙烯基}吡啶盐、 碘化(E,E)-N-甲基-2,6-二{2-[5’-(2-二茂铁乙烯基)-2,2’-联噻吩-5-基]乙烯基}吡啶盐、碘化(E,E)-N-甲基-2,4,6-三{2-[5’-(2-二茂铁乙烯基)-2,2’-联噻吩-5-基]乙烯基}吡啶盐。初步研究了这些化合物的电化学性质,结果表明,该类多取代二茂铁吡啶盐具有很好的氧化-还原可逆性,是潜在的电化学分子材料。     

Theoretical Investigation on the Electron and Energy Transfer between Peripheral Carrier Transport Groups and Central Chromophores in Electroluminescent Materials

The molecular materials with structures of luminescent core and peripheral carrier groups (e.g. carbazoles), have exhibited high‐performance in organic light‐emitting diodes (OLEDs). Present work is to understand the basic process of electronic and energy exchange between the peripheral functional groups and the central core through quantum chemical analysis. As an example, 4,7‐bis(9,9‐bis(6‐(9H‐carbazol‐9‐yl)hexyl)‐9H‐fluoren‐2‐yl)benzo[c]‐[1,2,5]thiadiazole (TCBzC) is investigated in regards to optoelectronic properties using density functional theory (DFT). The results suggest that the forbidden transition from peripheral carbazole to the central chromophore core makes for separated electrical and optical properties, and high performance electroluminescence (EL) is mainly attributed to the energy‐transfer from carbazoles to the fluorene derivative core     

18‐Crown‐6 Catalyzed Microwave‐mediated Synthesis of Symmetric Bis‐Heterocyclic Compounds under Solvent‐free Condition

An efficient, solvent‐free and 18‐crown‐6 catalyzed method for the synthesis of N‐alkyl‐4‐(4‐(5‐(2‐(alkyl‐amino)thiazol‐4‐yl)pyridin‐3‐yl)phenyl)thiazol‐2‐amine, N‐alkyl‐4‐(5‐(2‐alkyamino)thiazol‐4‐yl)pyridine‐3‐yl)thiazol‐2‐amine, and 4,4′‐bis‐{2‐[amino]‐4‐thiazolyl}biphenyl bis‐heterocyclic derivatives via microwave accelerated cyclization is presented.     

Synthesis,crystal structures,antiproliferative activities and reverse docking studies of eight novel Schiff bases derived from benzil

Eight novel Schiff bases derived from benzil dihydrazone ( BDH ) or benzil monohydrazone ( BMH ) and four fused‐ring carbonyl compounds (3‐formylindole, FI ; 3‐acetylindole, AI ; 3‐formyl‐1‐methylindole, MFI ; 1‐formylnaphthalene, FN ) were synthesized and characterized by elemental analysis, ESI–QTOF–MS, ¹H and ¹³C NMR spectroscopy, as well as single‐crystal X‐ray diffraction. They are (1Z,2Z)‐1,2‐bis{(E)‐[(1H‐indol‐3‐yl)methylidene]hydrazinylidene}‐1,2‐diphenylethane ( BDHFI ), C₃₂H₂₄N₆, (1Z,2Z)‐1,2‐bis{(E)‐[1‐(1H‐indol‐3‐yl)ethylidene]hydrazinylidene}‐1,2‐diphenylethane ( BDHAI ), C₃₄H₂₈N₆, (1Z,2Z)‐1,2‐bis{(E)‐[(1‐methyl‐1H‐indol‐3‐yl)methylidene]hydrazinylidene}‐1,2‐diphenylethane ( BMHMFI ) acetonitrile hemisolvate, C₃₄H₂₈N₆·0.5CH₃CN, (1Z,2Z)‐1,2‐bis{(E)‐[(naphthalen‐1‐yl)methylidene]hydrazinylidene}‐1,2‐diphenylethane ( BDHFN ), C₃₆H₂₆N₄, (Z)‐2‐{(E)‐[(1H‐indol‐3‐yl)methylidene]hydrazinylidene}‐1,2‐diphenylethanone ( BMHFI ), C₂₃H₁₇N₃O, (Z)‐2‐{(E)‐[1‐(1H‐indol‐3‐yl)ethylidene]hydrazinylidene}‐1,2‐diphenylethanone ( BMHAI ), C₂₄H₁₉N₃O, (Z)‐2‐{(E)‐[(1‐methyl‐1H‐indol‐3‐yl)methylidene]hydrazinylidene}‐1,2‐diphenylethanone ( BMHMFI ), C₂₄H₁₉N₃O, and (Z)‐2‐{(E)‐[(naphthalen‐1‐yl)methylidene]hydrazinylidene}‐1,2‐diphenylethanone ( BMHFN ) C₂₅H₁₈N₂O. Moreover, the in vitro cytotoxicity of the eight title compounds was evaluated against two tumour cell lines (A549 human lung cancer and 4T₁ mouse breast cancer) and two normal cell lines (MRC‐5 normal lung cells and NIH 3T3 fibroblasts) by MTT assay. The results indicate that four ( BDHMFI , BDHFN , BMHMFI and BMHFN ) are inactive and the other four ( BDHFI , BDHAI , BMHFI and BMHAI ) show severe toxicities against human A549 and mouse 4T₁ cells, similar to the standard cisplatin. All the compounds exhibited weaker cytotoxicity against normal cells than cancer cells. The Swiss Target Prediction web server was applied for the prediction of protein targets. After analyzing the differences in frequency hits between these active and inactive Schiff bases, 18 probable targets were selected for reverse docking with the Surflex‐dock function in SYBYL‐X 2.0 software. Three target proteins, i.e. human ether‐á‐go‐go‐related (hERG) potassium channel, the inhibitor of apoptosis protein 3 and serine/threonine‐protein kinase PIM1, were chosen as the targets. Finally, the ligand‐based structure–activity relationships were analyzed based on the putative protein target (hERG) docking results, which will be used to design and synthesize novel hERG ion channel inhibitors.     

2,6‐Bis(azaindole)pyridine: reactivity with iron(III) and copper(II) salts

1‐[6‐(1H‐Pyrrolo[2,3‐b]pyridin‐1‐yl)pyridin‐2‐yl]‐1H‐pyrrolo[2,3‐b]pyridin‐7‐ium tetrachloridoferrate(III), (C₁₉H₁₄N₅)[FeCl₄], (II), and [2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl‐κN⁷)pyridine‐κN]bis(nitrato‐κO)copper(II), [Cu(NO₃)₂(C₁₉H₁₃N₅)], (III), were prepared by self‐assembly from FeCl₃·6H₂O or Cu(NO₃)₂·3H₂O and 2,6‐bis(1H‐pyrrolo[2,3‐b]pyridin‐1‐yl)pyridine [commonly called 2,6‐bis(azaindole)pyridine, bap], C₁₉H₁₃N₅, (I). Compound (I) crystallizes with Z′ = 2 in the P space group, with both independent molecules adopting a trans–trans conformation. Compound (II) is a salt complex with weak C—H...Cl interactions giving rise to a zigzag network with π‐stacking down the a axis. Complex (III) lies across a twofold rotation axis in the C2/c space group. The Cu^II center in (III) has an N₃O₂ trigonal–bipyramidal environment. The nitrate ligand coordinates in a monodentate fashion, while the bap ligand adopts a twisted tridentate binding mode. C—H...O interactions give rise to a ribbon motif.     

Medium band gap conjugated polymers from thienoacene derivatives and pentacyclic aromatic lactam as promising alternatives of poly(3‐hexylthiophene) in photovoltaic application

Two alternating medium band gap conjugated polymers (PBDT‐TPTI and PDTBDT‐TPTI) derived from 4,8‐bis(4,5‐dioctylthien‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT‐T) or 5,10‐bis(4,5‐didecylthien‐2‐yl)dithieno[2,3‐d:2′,3′‐d′]benzo[1,2‐b:4,5‐b′]dithiophene (DTBDT‐T) with pentacyclic aromatic lactam of N,N‐didodecylthieno[2′,3′:5,6]pyrido[3,4‐g]thieno[3,2‐c]‐iso‐quinoline‐5,11‐dione (TPTI), are synthesized and characterized. The comparative investigation of the photostabilities of the copolymers revealed that the PDTBDT‐TPTI film exhibited the comparable photostability in relative to P3HT. Meanwhile, the inverted photovoltaic cells (i‐PVCs) from the blend films of PBDT‐TPTI and/or PDTBDT‐TPTI with PC₇₁BM, in which poly[(9,9‐bis(3′‐(N,N‐dimethylamino)propyl)‐2,7‐fluorene)‐alt‐2,7‐(9,9‐dioctylfluorene)] were used as cathode modifying interlayer, presented higher power conversion efficiencies (PCEs) of 5.98% and 6.05% with photocurrent response ranging from 300 nm to 650 nm in contrast with the PCEs of 4.48% for the optimal inverted PVCs from P3HT/PC₇₁BM under AM 1.5 G 100 mW/cm². The PCEs of the i‐PVCs from PBDT‐TPTI and PDTBDT‐TPTI were improved to 7.58% and 6.91% in contrast to that of 0.02% for the P3HT‐based i‐PVCs, and the photocurrent responses of the devices were extended to 300–792 nm, when the ITIC was used as electron acceptor materials. The results indicate that the PBDT‐TPTI and PDTBDT‐TPTI can be used as the promising alternatives of notable P3HT in the photovoltaic application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 85–95     

Synthesis and electrochromic properties of triphenylamine containing copolymers: Effect of π‐bridge on electrochemical properties

In this study, a series of benzotriazole (BTz) and triphenylamine (TPA)‐based random copolymers; poly4‐(5‐(2‐dodecyl‐7‐methyl‐2H‐benzo[d][1,2,3]triazol‐4‐yl)thiophen‐2‐yl)‐N‐(4‐(5‐methylthiophen‐2‐yl)phenyl)‐N‐phenylaniline ( P1 ), poly4′‐(2‐dodecyl‐7‐methyl‐2H‐benzo[d][1,2,3]triazol‐4‐yl)‐N‐(4′‐methyl‐[1,1′‐biphenyl]‐4‐yl)‐N‐phenyl‐[1,1′‐biphenyl]‐4‐amine ( P2 ), and poly4‐(5′‐(2‐dodecyl‐7‐(5‐methylthiophen‐2‐yl)?2H‐benzo[d][1,2,3]triazol‐4‐yl)‐[2,2′‐bithiophen]‐5‐yl)‐N‐(4‐(5‐methylthiophen‐2‐yl)phenyl)‐N‐phenylaniline ( P3 ) were synthesized to investigate the effect of TPA unit and π‐bridges on electrochemical and spectroelectrochemical properties of corresponding polymers. The synthesis was carried out via Stille coupling for P1 , P3 , and Suzuki coupling for P2 . Electrochemical and spectral results showed that P1 has an ambipolar character, in other words it is both p‐type and n‐type dopable, whereas P2 and P3 have only p‐doping property. Effect of different π‐bridges and TPA unit on the HOMO and LUMO energy levels, switching time, and optical contrast were discussed. All polymers are promising materials for electrochromic devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 537–544     

Biphenyl‐ and phenylnaphthalenyl‐substituted 1H‐imidazole‐4,5‐dicarbonitrile catalysts for the coupling reaction of nucleoside methyl phosphonamidites

Crystal structures are reported for three substituted 1H‐imidazole‐4,5‐dicarbonitrile compounds used as catalysts for the coupling reaction of nucleoside methyl phosphonamidites, namely 2‐(3′,5′‐dimethylbiphenyl‐2‐yl)‐1H‐imidazole‐4,5‐dicarbonitrile, C₁₉H₁₄N₄, (I), 2‐(2′,4′,6′‐trimethylbiphenyl‐2‐yl)‐1H‐imidazole‐4,5‐dicarbonitrile, C₂₀H₁₆N₄, (II), and 2‐[8‐(3,5‐dimethylphenyl)naphthalen‐1‐yl]‐1H‐imidazole‐4,5‐dicarbonitrile, C₂₃H₁₆N₄, (III). The asymmetric unit of (I) contains two independent molecules with similar conformations. There is steric repulsion between the imidazole group and the terminal phenyl group in all three compounds, resulting in the nonplanarity of the molecules. The naphthalene group of (III) shows significant deviation from planarity. The C—N bond lengths in the imidazole rings range from 1.325 (2) to 1.377 (2) Å. The molecules are connected into zigzag chains by intermolecular N—H...N_imidazole [for (I)] or N—H...·N_cyano [for (II) and (III)] hydrogen bonds.     

Synthesis and Characteristics of Organic Red‐Emissive Materials Based on Phenanthro[9,10‐d]imidazole

Red emission is one of the three primary colors that are essential for the realization of full‐color displays and solid‐state lightings. A high solid‐state efficiency is a crucial factor for the applications in organic light‐emitting diodes (OLEDs). In this work, two new donor‐acceptor‐donor type phenanthro[9,10‐d]imidazole (PIM)‐based derivatives, (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenyl)acrylonitrile) ( PIDSB ) and 2,3‐bis(4′‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)‐[1,1′‐biphenyl]‐4‐yl)fumaronitrile ( PIDPh ), are designed and synthesized. Both of them possess high thermal stabilities. PIDPh shows typical characteristics of aggregation‐induced emission enhancement, while PIDSB displays an aggregation‐caused quenching effect. They both exhibit significant red‐shifted emissions compared with PIM owing to intramolecular charge transfer. In the film state, the emission peaks of PIDSB and PIDPh are located at 538 nm and 605 nm with high photoluminescent quantum yields of 63.82 % and 41.26 %, respectively. The non‐doped OLED using PIDPh as the active layer shows the maximum external quantum efficiency of 2.06 % with a very low efficiency roll‐off, and exhibits the electroluminescent peak at 640 nm with a Commission Internationale de l′Éclairage coordinate of (0.617,0.396), meeting well the criteria of red OLEDs.     

In situ synthesis of mononuclear copper(II) complexes of the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine

Two mononuclear copper complexes, {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN²)methyl]amine‐κN}(3,5‐dimethyl‐1H‐pyrazole‐κN²)(perchlorato‐κO)copper(II) perchlorate, [Cu(ClO₄)(C₅H₈N₂)(C₁₂H₁₉N₅)]ClO₄, (I), and {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN²)methyl]amine‐κN}bis(3,5‐dimethyl‐1H‐pyrazole‐κN²)copper(II) bis(hexafluoridophosphate), [Cu(C₅H₈N₂)₂(C₁₂H₁₉N₅)](PF₆)₂, (II), have been synthesized by the reactions of different copper salts with the tripodal ligand tris[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (TDPA) in acetone–water solutions at room temperature. Single‐crystal X‐ray diffraction analysis revealed that they contain the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (BDPA), which cannot be obtained by normal organic reactions and has thus been captured in the solid state by in situ synthesis. The coordination of the Cu^II ion is distorted square pyramidal in (I) and distorted trigonal bipyramidal in (II). The new in situ generated tridentate BDPA ligand can act as a meridional or facial ligand during the process of coordination. The crystal structures of these two compounds are stabilized by classical hydrogen bonding as well as intricate nonclassical hydrogen‐bond interactions.     

Relative Electrophilic Fluorinating Power as Assayed by Competitive Catalytic Halogenation Reactions

Catalytic fluorination/chlorination competition experiments of β‐keto ester 5 were used to assess the relative fluorinating activity of various electrophilic N? F reagents (containing an N? F bond). Thus, in the halogenation reactions catalyzed by the [Ti(TADDOLato)] complex 1 (=bis(acetonitrile)dichloro[(4R,5R)‐2,2‐dimethyl‐α,α,α′,α′‐tetra(naphthalen‐1‐yl)‐1,3‐dioxolane‐4,5‐dimethanolato(2?)‐κO,κO′]titanium), the activity range of a series of commercially available reagents spans more than two orders of magnitude. Selectfluor^TM (=1‐(chloromethyl)‐4‐fluoro‐1,4‐diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate); 9 ; also called F‐TEDA; TEDA=triethylenediamine) reacts more than 100 times faster than 1‐fluoropyridinium tetrafluoroborate.     

Synthesis and Photovoltaic Properties of Thieno[3,4‐c]pyrrole‐4,6‐dione‐based donor–acceptor Copolymers

Three donor–acceptor (D–A) 1,3‐di(thien‐2‐yl)thieno [3,4‐c]pyrrole‐4,6‐dione‐based copolymers, poly{9,9‐dioctylfluorene‐2,7‐diyl‐alt‐1,3‐bis(4‐hexylthien‐2‐yl)‐5‐octylthieno[3,4‐c]pyrrole‐4,6‐dione}, poly{N‐(1‐octylnonyl)carbazole‐2,7‐diyl‐alt‐1,3‐bis(4‐hexylthien‐2‐yl)‐5‐octylthieno[3,4‐c]pyrrole‐4,6‐dione}, and poly {4,8‐bis(2‐ethylhexyloxyl) benzo[1,2‐b:3,4‐b′]dithiophene‐alt‐1,3‐bis(4‐hexylthien‐2‐yl)‐5‐octylthieno[3,4‐c] pyrrole‐4,6‐dione} were synthesized by Suzuki or Stille coupling reaction. By changing the donor segment, the bandgaps and energy levels of these copolymers could be finely tuned. Cyclic voltammetric study shows that the highest occupied molecular orbital (HOMO) energy levels of the three copolymers are deep‐lying, which implies that these copolymers have good stability in the air and the relatively low HOMO energy level assures a higher open‐circuit potential when they are used in photovoltaic cells. Bulk‐heterojunction photovoltaic cells were fabricated with these polymers as the donors and PC₇₁BM as the acceptor. The cells based on the three copolymers exhibited power conversion efficiencies of 0.22, 0.74, and 3.11% with large open‐circuit potential of 1.01, 0.99, and 0.90 V under one sun of AM 1.5 solar simulator illumination (100 mW/cm²). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Structural studies of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine hetero‐scorpionate copper complexes

The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the Cu^I and Cu^II oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C₁₅H₁₇N₃)]·0.18H₂O, (1), catena‐poly[[copper(I)‐μ₂‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ⁵N,N′,N′′:C²,C³] perchlorate acetonitrile monosolvate], {[Cu(C₁₅H₁₇N₃)]ClO₄·CH₃CN}_n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl₂(C₁₅H₁₇N₃)]·CH₂Cl₂, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II) perchlorate, [CuCl(C₁₅H₁₇N₃)]ClO₄, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu₂Cl₂(C₁₅H₁₇N₃)₂][(C₆H₅)₄B]₂, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two Cu^I complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the Cu^I atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with Cu^II show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu₂Cl₂ moiety.