Formation of T‐Shaped versus Charge‐Transfer Molecular Adducts in the Reactions Between Bis(thiocarbonyl) Donors and Br2 and I2

The reactions of 4,5,6,7‐tetrathiocino‐[1,2‐b:3,4‐b′]‐1,3,8,10‐tetrasubstituted‐diimidazolyl‐2,9‐dithiones (R₂,R′₂‐todit; 1 : R=R′=Et; 2 : R=R′=Ph; 3 : R=Et, R′=Ph) with Br₂ exclusively afforded 1:1 and 1:2 “T‐shaped” adducts, as established by FT‐Raman spectroscopy and single‐crystal X‐ray diffraction in the case of complex 1? 2 Br₂. On the other hand, the reactions of compounds 1 – 3 with molecular I₂ provided charge‐transfer (CT) “spoke” adducts, among which the solvated species 3? 2 I₂ ? (1?x)I₂ ? x CH₂Cl₂ (x=0.94) and ( 3 )₂ ? 7 I₂ ? x CH₂Cl_2, (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT‐Raman spectroscopy and supported by theoretical calculations at the DFT level.     

Mononuclear vs. binuclear carboxylates of copper(II) with 2,2′‐bipyridine: Synthesis,characterization, structural description,and properties

Two new copper(II) carboxylate complexes with 2,2′‐bipyridine and para‐nitrophenyl acetate (complex 1 ) and phenyl acetate (complex 2 ) have been synthesized; isolated in quantitative yield; and characterized using fourier‐transform infrared spectroscopy (FT‐IR), electron paramagnetic resonance, absorption spectroscopy, electrochemistry, and powder and single crystal X‐ray diffraction (XRD) techniques. Being mononuclear, the geometry around copper in complex 1 is a Jahn–Teller distorted octahedral, while complex 2 is binuclear with slightly distorted square pyramidal geometry around both copper ions. Powder XRD indicated several peaks in spectra of both complexes, which coincided with their theoretical spectra. FT‐IR results of the carboxylate stretching frequency were in accordance with the single crystal structure data. Electron paramagnetic resonance spectra of complexes 1 and 2 yielded g_┴ values of 2.06161 and 2.24623 and 1.94959, respectively, indicating a localized electron in b₁ (d _x²_–y²‐orbital). Ultra‐violet (UV)–visible spectroscopy and electrochemistry helped in characterization, as well as in deoxyribonucleic acid (DNA)‐binding ability of the complexes, yielding DNA‐binding constant values = 1.351 × 10⁴ and 1.361 × 10⁴ and 1.820 × 10⁴ and 2.426 × 10⁴ M^?1, respectively, for complexes 1 and 2 . The complexes demonstrate good biological potential.     

A Dual Plating Battery with the Iodine/[ZnIx(OH2)4−x]2−x Cathode

Plating battery electrodes typically deliver higher specific capacity values than insertion or conversion electrodes because the ion charge carriers represent the sole electrode active mass, and a host electrode is unnecessary. However, reversible plating electrodes are rare for electronically insulating nonmetals. Now, a highly reversible iodine plating cathode is presented that operates on the redox couples of I₂/[ZnI_x(OH₂)_4?x]^2?x in a water‐in‐salt electrolyte. The iodine plating cathode with the theoretical capacity of 211 mAh g^?1 plates on carbon fiber paper as the current collector, delivering a large areal capacity of 4 mAh cm^?2. Tunable femtosecond stimulated Raman spectroscopy coupled with DFT calculations elucidate a series of [ZnI_x(OH₂)_4?x]^2?x superhalide ions serving as iodide vehicles in the electrolyte, which eliminates most free iodide ions, thus preventing the consequent dissolution of the cathode‐plated iodine as triiodides.     

Three Distinct Silver(I) Coordination Polymers: Bridging‐­Ligand Directed Syntheses,Crystal Structures,Luminescence, and Nitrobenzene Sensing Properties

Three distinct Ag^I‐DMAP [DMAP = 4‐(dimethylamino)pyridine] coordination polymers [Ag₂I₂(DMAP)₂]_n ( 1 ), [Ag₂(CN)₂(DMAP)_2.5 · DMAP]_n ( 2 ), and [Ag(SCN)(DMAP)]_n ( 3 ) were constructed by monatomic I^–, diatomic CN^–, and triatomic SCN^– bridges, respectively. 1 – 3 were determined by FT‐IR spectroscopy, elemental analyses, TGA, powder and single‐crystal X‐ray diffraction. 1 exhibits a 1D wavelike chain structure, sustained by 3‐connected I^– bridges, whereas 2 shows a unique 1D single‐ and double‐strand alternating chain, supported by 3‐connected CN^– bridges. Compound 3 has a 2D 3‐connected network architecture, fabricated by 3‐connected SCN^– bridges, and exhibits a (4 · 8²) topology. The luminescence and nitrobenzene sensing properties of 1 – 3 were explored in 2‐propanol suspensions, which revealed that compounds 1 – 3 exhibit DMAP originated luminescence emissions and are highly sensitive for nitrobenzene detection.     

Self‐Assembly of a Au16 Ring via Metal–Metal Bonding Interactions

Metal–metal bonding interactions have been employed as an efficient strategy to generate a number of unique gold(I) metallo‐macrocycles with fascinating functions. The self‐assembly, crystal structure and emission property of novel nest‐like tetramer 1₄ , namely, {[Au₄(μ‐dppm)₂(μ‐dctp^2?)](BF₄)₂}₄ ? (CH₃CN)₂ (dppm=bis(diphenylphosphino)methane, dctp^2?=N,N′‐bis(dicarbodithioate)‐2,11‐diaza[3.3]paracyclophane) is reported. The complex has been characterized by single‐crystal X‐ray diffraction analysis, ¹H NMR spectroscopy, ¹³C NMR spectroscopy, and CSI‐MS spectrometry. The aggregate demonstrates the sixteen gold(I) atoms are arranged in a ring with a circumference of 50.011(68) Å generated by Au^I???Au^I attractions. UV/visible and luminescence spectroscopy revealed that this Au^I???Au^I bonded metallo‐macrocycle exhibited yellow phosphorescence.     

Synthesis,Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: HoxSc3−xN@C80 (x=1, 2)

The synthesis, isolation and spectroscopic characterization of holmium‐based mixed metal nitride clusterfullerenes Ho_xSc_3?xN@C₈₀ (x=1, 2) are reported. Two isomers of Ho_xSc_3?xN@C₈₀ (x=1, 2) were synthesized by the reactive gas atmosphere method and isolated by multistep recycling HPLC. The isomeric structures of Ho_xSc_3?xN@C₈₀ (x=1, 2) were characterized by laser‐desorption time‐of‐flight (LD‐TOF) mass spectrometry and UV/Vis/NIR, FTIR and Raman spectroscopy. A comparative study of M_xSc_3?xN@C₈₀ (M=Gd, Dy, Lu, Ho) demonstrates the dependence of their electronic and vibrational properties on the encaged metal. Despite the distinct perturbation induced by 4f¹⁰ electrons, we report the first paramagnetic ¹³C NMR study on Ho_xSc_3?xN@C₈₀ (I; x=1, 2) and confirm I_h‐symmetric cage structure. A ⁴⁵Sc NMR study on HoSc₂N@C₈₀ (I, II) revealed a temperature‐dependent chemical shift in the temperature range of 268–308 K.     

Rhodium‐ and ruthenium‐complex‐catalyzed condensation of ferrocene‐containing dithiols and diols with diarylsilanes to give silaferrocenophanes and ferrocene polymers

1,1′‐Ferrocenedithiol reacts with di(4‐methoxyphenyl)silane, diphenylsilane, and di(4‐fluorophenyl)silane in the presence of RhCl(PPh₃)₃ catalyst to give mixtures of 2,2‐diaryl‐1,3‐dithia‐2‐sila[3]ferrocenophanes (1a–3a) and ? (Fc? S? SiAr₂? S) _n? (Fc = 1,1′‐ferrocenylene; 1b: Ar = C₆H₄OMe‐4; 2b: Ar = Ph; 3b: Ar = C₆H₄F‐4). The products are isolated and characterized by NMR spectroscopy and elemental analyses. The polymers 1b–3b, obtained from a toluene‐soluble fraction of the products, show GPC elution patterns corresponding to M_n values of 2700–4600 (polystyrene standards). The UV–vis spectra of the ferrocenophanes and polymers exhibit a d–d transition peak at about 440 nm, while the polymers show a π–π* transition peak at 320–330 nm. The cyclic voltammograms of 3a (Ar = C₆H₄F ? 4) and 3b show a reversible redox of the iron center at 0.27 V and 0.35 V (Ag⁺/Ag) respectively. Reaction of 1,1′‐ferrocenedimethanol with diphenylsilane in the presence of RuCl₂(PPh₃)₃ catalyst results in selective formation of 3,3‐diphenyl‐2,4‐dioxa‐3‐sila[5]ferrocenophane ( 4 ), whose structure was determined by X‐ray crystallography. Copyright © 2001 John Wiley & Sons, Ltd.     

In situ — High Temperature Mössbauer Spectroscopy of Iron Nitrides and Nitridoferrates

The stoichiometric iron nitrides γ′‐Fe₄N, ε‐Fe₃N and ζ‐Fe₂N were characterized by Mössbauer spectroscopy. The thermal decomposition of ε‐Fe₃N was studied in‐situ by means of a specially developed Mössbauer furnace. We found ε‐Fe₃N to γ′‐Fe₄N and ε‐Fe₃N_x (x ≥ 1.3) as decomposition products and determined the border of γ′/ε transformation at T ? 930 K. Mössbauer spectroscopy was applied to study in‐situ the thermal decomposition of the nitridometalate Li₃[Fe^IIIN₂] and the formation of Li₂[(Li_1‐xFe^I_x)N], the compound with the largest local magnetic field ever observed in an iron containing material. The kinetics of formation and the stability of Li₂[(Li_1‐xFe^I_x)N] was of particular interest in the present study.     

Ionic complexes of 1,1′‐dimethyltitanocene(IV) dichloride with simple α‐amino acids: synthesis,structural characterisation and investigation on hydrolytic stability in aqueous solution

Five cationic complexes of the general formula [Cp′₂Ti(A)₂]²⁺ [Cl^?]₂ [Cp′ = η⁵‐(CH₃)C₅H₄ and A = glycine, 1 ; 2‐methylalanine, 2 ; N‐methylglycine, 3 ; L ‐alanine, 4 ; and D ‐alanine 5 ] were prepared by the reaction of Cp′₂TiCl₂ and the appropriate α‐amino acid in 1:2 molar ratio from methanol–water solution in high yield. Air‐stable crystalline solids, highly soluble in water, were characterized by means of elemental analysis, IR, Raman, ¹H, ¹³C and ¹⁴N NMR spectroscopy. The structure of compound 3 was determined by single crystal X‐ray crystallography: orthorhombic Pbca No. 61, a = 9.5310(3), b = 18.2980(5), c = 26.6350(5) Å, V = 4654 ų, Z = 8. Hydrolytic stability of all compounds in D₂O was investigated using ¹H NMR spectroscopy within the pD interval of 2.9–6.5. All compounds slowly decomposed during 24 h at pD = 2.94, forming a mixture of hydrolytic products [Cp′₂Ti(A)(D₂O)]²⁺, [Cp′₂Ti(D₂O)₂]²⁺ and respective α‐amino acids. By elevating pD to 4.0 and up to 6.5, a yellowish precipitate was formed, which indicates decomposition of the complexes. These compounds were characterized using elemental analyses, IR and Raman spectroscopy and attributed to oligomeric and/or polymeric structures described empirically by the formula Ti(Cp′)_xO_y(OH)_z (x = 0.65; y = 0.3, z = 1.9). Copyright © 2005 John Wiley & Sons, Ltd.     

On the Structural Chemistry of γ‐Brasses: Two Different Interpenetrating Networks in Ternary F‐Cell Pd–Zn–Al Phases

Novel ternary phases, (Pd_1?xZn_x)₁₈(Zn_1?yAl_y)_86?δ (0≤x≤0.162, 0.056≤y≤0.088, 0≤δ≤4), which adopt a superstructure of the γ‐brass type (called γ′‐brass), have been synthesized from the elements at 1120 K. Single‐crystal X‐ray structural analysis reveals a phase width (F$\bar 4$ 3m, a=18.0700(3)–18.1600(2) Å, Pearson symbols cF400–cF416), which is associated with structural disorder based on both vacancies as well as mixed site occupancies. These structures are constructed of four independent 26‐atom γ‐clusters per primitive unit cells and centered at the four special positions A (0, 0, 0), B (1/4, 1/4, 1/4), C (1/2, 1/2, 1/2) and D (3/4, 3/4, 3/4). Two of these, centered at B and C , are completely ordered Pd₄Zn₂₂ clusters, whereas the other two, centered at A and D , contain all structural disorder in the system. According to our single‐crystal X‐ray results, Al substitutions are restricted to the A ‐ and D ‐centered clusters. Moreover, the outer tetrahedron (OT) site of the 26‐atom cluster at D is completely vacant at the Al‐rich boundary of these phases. Electronic structure calculations, using the tight‐binding linear muffin‐tin orbital atomic‐spheres approximation (TB‐LMTO‐ASA) method, on models of these new, ternary γ′‐brass phases indicate that the observed chemical compositions and atomic distributions lead to the presence of a pseudogap at the Fermi level in the electronic density of states curves, which is consistent with the Hume‐Rothery interpretation of γ‐brasses, in general.     

Enantiomeric bis(μ‐N,N′‐hexamethylenedisalicylaldiminato)dicopper(II) complexes

The title dimeric complex, bis{μ‐2,2′‐[hexane‐1,6‐diyl­bis(nitrilo­methyl­idyne)]­diphenolato‐1:2κ⁴O,N:N′,O′}dicopper(II),[Cu₂(C₂₀H₂₂N₂O₂)₂], has been investigated by single‐crystal X‐ray diffraction, by thermogravimetric analysis and differential scanning calorimetry, and also by FT–IR spectroscopy. Different synthetic and crystallization procedures gave crystals which were quite different in appearance, and it was initially thought that these were different polymorphic forms. Subsequent structure determination showed, in fact, serendipitous preparation of crystals in the P4₁ space group by one method and in space group P4₃ by the other. In these enantiomorphic structures, the Cu atoms have a distorted flattened tetrahedral coordination, with Cu—N and Cu—O distances in the ranges 1.954 (4)–1.983 (4) and 1.887 (4)–1.903 (4) Å, respectively.     

Darstellung und Charakterisierung von Iodoplatinaten MexNH4–xPtI4 (x = 2 − 4), gemischtvalenten Octaiododiplatinaten(II,IV) mit Pt2I8-Baugruppen

Preparation and Characterization of Iodoplatinates Me_xNH_4–xPtI₄ (x = 2–4), Mixed Valence Octaiododiplatinates(II,IV) with Pt₂I₈ Groups Iodoplatinates APtI₄ (A = Me_xNH_4–x with x = 2–4) have been prepared by partial oxidation of the correspondent hexaiododiplatinates(II) A₂Pt₂I₆ with I₂ in methanolic solutions. X-ray structure analyses of the bronze-coloured needle-shaped crystals of the compounds showed rows of dinuclear anions Pt₂I₈^2?, built up by edgesharing planar PtI₄ groups with Pt^II und octahedral PtI₆ groups with Pt^IV. The different space requirement of the cations leads to the formation of three different structures. Within the anion stacks weak intermolecular Pt^IV? I …? Pt^II interactions are detectable by Raman spectroscopy.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Two Robust Porous Metal–Organic Frameworks Sustained by Distinct Catenation: Selective Gas Sorption and Single‐Crystal‐to‐Single‐Crystal Guest Exchange

Assembly of copper(I) halide with a new tripodal ligand, benzene‐1,3,5‐triyl triisonicotinate (BTTP4), afforded two porous metal–organic frameworks, [Cu₂I₂(BTTP4)]?2 CH₃CN ( 1? 2 CH₃CN) and [CuBr(BTTP4)]?(CH₃CN ? CHCl₃ ? H₂O) ( 2? solvents), which have been characterized by IR spectroscopy, thermogravimetry (TG), single‐crystal, and powder X‐ray diffraction (PXRD) methods. Compound 1.CH3CN is a polycatenated 3D framework that consists of 2D (6,3) networks through inclined catenation, whereas 2 is a doubly interpenetrated 3D framework possessing the ThSi₂‐type ( ths ) (10,3)‐b topology. Both frameworks contain 1D channels of effective sizes 9×12 and 10×10 Ų, which amounts to 43 and 40 % space volume accessible for solvent molecules, respectively. The TG and variable‐temperature PXRD studies indicated that the frameworks can be completely evacuated while retaining the permanent porosity, which was further verified by measurement of the desolvated complex [Cu₂I₂(BTTP4)] ( 1′ ). The subsequent guest‐exchange study on the solvent‐free framework revealed that various solvent molecules can be adsorbed through a single‐crystal‐to‐single‐crystal manner, thus giving rise to the guest‐captured structures [Cu₂I₂(BTTP4)]?C₆H₆ ( 1.benzene ), [Cu₂I₂(BTTP4)]?2 C₇H₈ ( 1.2toluene ), and [Cu₂I₂(BTTP4)]?2 C₈H₁₀ ( 1.2ethyl benzene ). The gas‐adsorption investigation disclosed that two kinds of frameworks exhibited comparable CO₂ storage capacity (86–111 mL g^?1 at 1 atm) but nearly none for N₂ and H₂, thereby implying its separation ability of CO₂ over N₂ and H₂. The vapor‐adsorption study revealed the preferential inclusion of aromatic guests over nonaromatic solvents by the empty framework, which is indicative of selectivity toward benzene over cyclohexane.     

Reaction of N‐Heterocyclic Silylenes with Thioketone: Formation of Silicon–Sulfur Three (Si‐C‐S)‐ and Five (Si‐C‐C‐C‐S)‐Membered Ring Systems

Three‐ and five‐membered rings that bear the (Si‐C‐S ) and (Si‐C‐C‐C‐S ) unit have been synthesized by the reactions of L SiCl ( 1 ; L =PhC(NtBu)₂) and L′ Si ( 2 ; L′ =CH{(C?CH₂)(CMe)(2,6‐iPr₂C₆H₃N)₂}) with the thioketone 4,4′‐bis(dimethylamino)thiobenzophenone. Treatment of 4,4′‐bis(dimethylamino)thiobenzophenone with L SiCl at room temperature furnished the [1+2]‐cycloaddition product silathiacyclopropane 3 . However, reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si at low temperature afforded a [1+4]‐cycloaddition to yield the five‐membered ring product 4 . Compounds 3 and 4 were characterized by NMR spectroscopy, EIMS, and elemental analysis. The molecular structures of 3 and 4 were unambiguously established by single‐crystal X‐ray structural analysis. The room‐temperature reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si resulted in products 4 and 5 , in which 4 is the dearomatized product and 5 is formed under the 1,3‐migration of a hydrogen atom from the aromatic phenyl ring to the carbon atom of the C? S unit. Furthermore, the optimized structures of probable products were investigated by using DFT calculations.     

Syntheses,Crystal Structures,and Properties of Lead(II), ­Zinc(II), and Manganese(II) Complexes Constructed from 2, 3, 5, 6‐Tetraiodo‐1, 4‐benzenedicarboxylic Acid

Three new coordination compounds, [Pb(HBDC‐I₄)₂(DMF)₄]( 1 ) and [M(BDC‐I₄)(MeOH)₂(DMF)₂]_n (M = Zn^II for 2 and Mn^II for ( 3 ) (H₂BDC‐I₄ = 2, 3, 5, 6‐tetraiodo‐1, 4‐benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X‐ray single crystal structure analysis. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two‐dimensional (2D) layer through intermolecular O–H ··· O and C–H ··· O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P2₁/c and have similar one‐dimensional (1D) chain structures that are extended into three‐dimensional (3D) supramolecular networks by interchain C–H ··· π interactions. The Pb^II and Zn^II complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions.     

Synthesis,spectral investigation and biological interphase of drug‐based cytotoxic square pyramidal coordination compounds

We have synthesized ciprofloxacin‐based metal complexes of bipyridine derivatives [Cu(CFL)(Aⁿ)Cl].2H₂O (where CFL = ciprofloxacin and A = bipyridines e.g. A¹ = 4‐(4‐fluorophenyl)‐6‐p‐tolyl‐2,2′‐bipyridine, A⁶ = 4‐(4‐(benzyloxy)phenyl)‐6‐(4‐bromophenyl)‐2,2′‐bipyridine, etc.). The ligands and complexes were characterized using analytical (C, H, N elemental analysis, TGA and magnetic measurement) and spectroscopic methods (¹H and ¹³C NMR, FT‐IR, fast atom bombardment mass and reflectance spectroscopy). The products were evaluated by screening for DNA interaction activity on herring sperm DNA and studies suggest intercalative mode of DNA binding. The antimicrobial activity was determined in terms of minimum inhibitory concentration. Superoxide dismutase mimic studies were performed using the NADH/PMS/NBT system. The brine shrimp bioassay was also carried out to study the in vitro cytotoxic properties of the synthesized metal complexes. Copyright © 2012 John Wiley & Sons, Ltd.     

A Series of Polyoxometalate-Viologen Photochromic Materials for UV Probing,Amine Detecting and Inkless and Erasable Printing

In this work, by using two kinds of viologen ligands three POM-based Compounds were obtained under hydrothermal conditions, namely [Ag^I(bmypd)_0.5(β-Mo₈O₂₆)_0.5] (1) (bmypd ⋅ 2Cl=1,1′-[Biphenyl-4,4′-bis(methylene)]bis(4,4′-bipyridyinium)dichloride), [Ag^I₂(bypy)₄(HSiW₁₂O₄₀)₂] ⋅ 14H₂O (2) and [Ag^I(bypy)(γ-Mo₈O₂₆)_0.5] (3) (bypy⋅Cl=1-Benzyl-4,4′-bipyridyinium chloride). The structures were characterized by Fourier transform infrared spectroscopy (FT–IR), Powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction. Compounds 1–3 show excellent photochromic ability with fast photoresponse under the irradiation of ultraviolet light with different degrees of color changes. So compounds 1–3 can be used as visible ultraviolet detectors. Compounds 1–3 also possess photoluminescence properties with fast and excellent fluorescence quenching effect. Compounds 1–3 also can be used as inkless and erasable printing materials with suspensions of 1–3 applied to filter paper. Compounds 1–3 can also produce color changes in amine vapor environment, especially in an NH₃ atmosphere. Compounds 1–3 can be used as organic amine detectors.     

Synthesis,Crystal Structure,Photophysical and Electrochemical Properties of rac‐6,13‐Dihydro‐6,13‐methanopentacene

The title compound, rac‐6,13‐dihydro‐6,13‐methanopentacene ( 1 ), has been synthesized and characterized by elemental analysis, FT‐IR, ¹H NMR, UV‐Vis, HRMS spectra, cyclic voltammetry and single‐crystal X‐ray diffraction. The crystal belongs to orthorhombic, space group P2₁2₁2₁, with Z = 4 and cell dimensions a = 6.0185(4), b = 8.1914(6), c = 31.4080(19) Å. In the crystal structure, two types of intermolecular C–H···π hydrogen bonds are observed, and further stabilize the crystal structure. Its photophysical and electrochemical properties and complementary density functional theory (DFT) calculations are reported.     

Two isomorphous benzene­sulfon­amide crystal structures determined by intermolecular C—H⃛O,C—H⃛π and C—H⃛Cl interactions

The title compounds, N‐[5‐(4‐chloro­phenyl)­furan‐2‐yl­methyl]‐4‐methyl‐N‐(prop‐2‐ynyl)­benzene­sulfon­amide, (Ia), and N‐[5‐(2‐chloro­phenyl)­furan‐2‐yl­methyl]‐4‐methyl‐N‐(prop‐2‐ynyl)­benzene­sulfon­amide, (Ib), both C₂₁H₁₈ClNO₃S, have isomorphous crystal structures. The crystal packing is mainly determined by intermolecular C—H?O and C—H?π interactions. These interactions are very similar in (Ia) and (Ib). Additional intermolecular C—H?Cl interactions appear less important and are different in (Ia) and (Ib). The different positions of the Cl atoms result in small variations of the crystal packing of the two compounds.