Dicationic Salts Research Articles

Solution, thermal and optical properties of bis(pyridinium salt)s as ionic liquids

Bis(pyridinium salt)s containing different alkyl chain lengths and various organic counterions were prepared by the ring-transmutation reaction of bis(pyrylium tosylate) with aliphatic amines in dimethyl sulfoxide at 130–135 °C for 18 h and their tosylate counterions were exchanged to other anions such as triflimide, methyl orange, and dioctyl sulfosuccinate by the metathesis reaction in a common organic solvent. Their chemical structures were established by using 1H, 19F, and 13C NMR spectra. The thermal properties of bis(pyridinium salt)s were studied by DSC and TGA measurements. Some of the dicationic salts provided low melting points below 100 °C and some of them displayed amorphous properties. Polarized optical microscopy studies revealed the crystal structures prior to melting temperatures in some cases. Their optical properties were examined by using UV–Vis and photoluminescent spectrometers; and they emitted blue light both in the solution and solid states regardless of their microstructures, counterions, and the polarity of organic solvents. However, most of these salts exhibited hypsochromic shifts in their emission peaks in the solid state when compared with those of their solution spectra. Due to unique properties of methyl orange anion as a pH indicator, two of the salts showed different color change in varying concentrations of triflic acid in common organic solvents, demonstrating their potential use as an acid sensor in methanol, acetonitrile and acetone.

Hydrogen generation from the hydrolysis of sodium borohydride with new pyridinium dicationic salts containing transition metal complexes

Pyridinium based dicationic ionic salts [C6(mpy)2] containing transition metal halide anions [NiCl4]2− and [CoCl4]2− were synthesized and characterized by 1H NMR, 13C NMR, LRMS-MS & TGA. The catalytic activities of dicationic ionic liquids were studied for the first time in the hydrolysis reaction of sodium borohydride. The reported work includes the full experimental details for the collection of a wealth of kinetic data to determine the activation energy (Ea = 56.36 kJ/mol) and effects of the amount of catalyst, amount of substrate and temperature on the rate for the catalytic hydrolysis of NaBH4. The activation energy of the catalyst dicationic tetrachloronickelate (II) anion for hydrogen production is comparable to that of other metal halide catalysts.

Solvent-free Michael addition of 2-cyclohexenone under ultrasonic irradiation in the presence of long chain dicationic ammonium salts

Long chain dicationic ammonium salts (1a-1c), easily prepared from tert-amines and dihaloalkanes, were successfully used as efficient phase-transfer catalysts in the Michael addition reaction of various active methylene compounds to 2-cyclohexenone without solvent under ultrasonic irradiation. The investigated dicationic salts were more effective than monocationic tetrabutylammonium bromide, with short reaction times and high yields. This methodology was established under phase-transfer catalytic conditions and ultrasonic effects with many advantages, including the easy and cost-effective synthesis of the catalyst, mild reaction conditions, short reaction times, good yields, simple work-up procedures, and environmental friendliness.

Carcass maturity and dicationic salts affect preblended, low-fat, low-sodium restructured beef

Preblending A- and C-maturity muscles with MgCl 2 and/or CaCl 2 was investigated in low-fat, low-sodium restructured beef. Products were formulated to contain: 1) 80% chunks, preblended 12 h with 0.05% MgCl 2, 0.05% CaCl 2, or a combination of each (0.1%) and 0.4% sodium tripolyphosphate (STPP) and 2) 20% mince preblended 12 h with 0.05% of each dicationic salt or the combination of dicationic salts (0.1%), 0.4% STPP, and 1.0% NaCl. This formulation achieved a raw product NaCl content of 0.2%. Additionally, a control was formulated with chunks and mince that contained no dicationic salt. CaCl 2 decreased raw and cooked pH and cook yield, and increased cohesiveness; whereas, MgCl 2 increased cook yield and myosin solubility. Total protein solubility was not affected by muscle maturity or dicationic treatment. Myosin solubility of the combination treatment was greater for C-maturity muscle (57 months) compared to A-maturity muscle (20 months) formulations. Control, C-maturity muscle treatments contained more insoluble and total collagen ( p < 0.05), and these treatments were more cohesive ( p < 0.05) than control, A-maturity treatments. The combination of CaCl 2 and MgCl 2 increased hardness of A-maturity products, but it decreased hardness of C-maturity products. In addition to increasing hardness of A-maturity products, the combination treatment lowered ( p < 0.05) cook yield for these products.

Synthesis and properties of new tetrachlorocobaltate (II) and tetrachloromanganate (II) anion salts with dicationic counterions

New tetrachlorocobaltate (II) and tetrachloromanganate (II) ionic compounds containing various counterdications were synthesized and characterized. These salts are soluble in polar solvents such as methanol and water. Physical properties such as thermal stability, melting point, and magnetic susceptibility of these salts depend on the cation or anion structure. The thermal stability of the phosphinium or imidazolium based salts is higher than that of the pyridinium or triethylaminonium analogues. The melting point of these compounds is following the order of triphenylphosphinium > pyridinium > imidazolium dications, and symmetrical dicationic salts > unsymmetrical ones. The magnetic susceptibility ( χ M T values) of tetrachloromanganate (II) anions-based salts is higher than that of tetrachlorocobaltate (II) anions-based salts. These dicationic salts exhibit weak antiferromagnetic interactions and have higher magnetic susceptibility than that of the previously reported tetrachloromanganate (II) and tetrachlorocobaltate(II) salts with monocationic counterion.

Synthesis and properties of new (μ-oxo)bis[trichloroferrate(III)] dianion salts incorporated with dicationic moiety

New (μ-oxo)bis[trichloroferrate(III)] dianions-based ionic compounds that contain various counterdications were synthesized and characterized with regards to their crystal structures, thermal properties, and magnetic susceptibility. These salts are soluble in polar solvents such as methanol and water. The melting point of these compounds is affected by the dication following the order of triphenylphosphinium > pyridinium > imidazolium dications, and symmetrical dicationic salts > unsymmetrical ones. In these compounds, the trichloroferrate dianion exists in either a linear or a bent form, which is affected by the dications. Interestingly, the dicationic diferrate compounds show magnetic coupling constants fairly smaller than those reported in literature for diferrate salts in which monocations are the counterion. Furthermore, unlike the diferrate salts associated with separate monocations, the linear diferrate dicationic compounds show magnetic coupling constant lower than that of bent diferrate dicationic salts.

Bridged Heterocyclium Dicationic closo-Icosahedral Perfluoroborane, Borane, and Carborane Salts via Aqueous, Open-Air Benchtop Synthesis

Thirteen bridged triazolium and imidazolium dicationic salts, which uniquely pair closo-icosahedral perfluoroborane [B(12)F(12)](2-), borane [B(12)H(12)](2-), or carborane [CB(11)H(12)](-) anionic species with unsaturated bridged heterocyclium dications, were synthesized using an aqueous benchtop method. This considerably extends the scope of a reported aqueous synthesis of binary [heterocyclium](2)[B(12)H(12)] and [heterocyclium][CB(11)H(12)] salts. Also, the one-step preparation of five new precursor bridged heterocyclium dicationic dihalide salts using conventional procedures and in one case a microwave-assisted method is described.

Two-photon fluorescence imaging of DNA in living plant turbid tissue with carbazole dicationic salt

Three carbazole dicationic salts, namely 3,6-bis(1-methyl-4-vinylpyridinium) carbazole diiodide (BMVC), 9-ethyl-3,6-bis(1-methyl-4-vinylpyridinium) carbazole diiodide (9E-BMVC) and 9-ethyl-3,6-bis(1-hydroxyethyl-4-vinylpyridinium)carbazole diiodide (9E-BHVC), were synthesized successfully. Their photophysical properties were evaluated by absorption, one- and two-photon fluorescence spectra, and their higher fluorescence intensity and larger two-photon excited fluorescence action cross-sections (Φ×δ) in the presence of DNA than those in the absence of DNA give them good DNA two-photon light-switch properties. Furthermore, their ability to image nuclei in living plant cells and turbid tissues by using two-photon excited fluorescence was carefully studied, and the experimental results indicate that these dicationic salts can exclusively label nuclei in intact living plant cells and tissues. In particular, 9E-BHVC exhibits optimized DNA labeling performance. Very importantly, compared to DAPI, 9E-BHVC can be used to carry out deeper observation using the same incident power, or can be used to obtain usable fluorescent images by using a lower incident power.

A Versatile Synthesis of Electroactive Stilbenoprismands for Effective Binding of Metal Cations

A versatile synthesis of a new class of polyaromatic receptors (stilbenoprismands) containing a Delta-shaped cavity similar to that of the pi-prismand together with an intimately coupled electroactive stilbenoid moiety was accomplished via an efficient intramolecular McMurry coupling reaction. The presence of the Delta-shaped cavity in stilbenoprismands allows an efficient binding of a single silver cation as probed by (1)H NMR spectroscopy. Electron-rich stilbenoprismands undergo a ready oxidation to their highly robust cation-radical and dicationic salts. X-ray structure determination of a representative dicationic stilbenoprismand showed that the charges were largely localized on the tetraarylethylene moiety, which results in a twisting of the ethylenic C=C bond by approximately 35 degrees. Moreover, the electronic coupling among the stilbenoid and pi-prismand moieties in various stilbenoprismands was briefly probed by optical methods.

Textural properties and microstructure of low-fat and sodium-reduced meat batters formulated with gellan gum and dicationic salts

Instrumental texture characteristics of low-fat, reduced-sodium meat batters formulated with other salts (KCl and MgCl 2 or CaCl 2) with gellan gum were evaluated. Fat and sodium reduction through incorporation of gellan gum and either of the dicationic salts produced less rigid, more ductile structures. Inclusion of magnesium chloride resulted in better performance, whereas addition of calcium chloride resulted in less desirable properties. The dicationic salts level used probably inhibited the gellan gum thermoreversible properties, affecting its water holding properties. Microstructural differences between the dicationic salt treatments were apparently due to the effect of dicationic salt concentration on myofibrillar protein extraction and solubilization, and gellan gum gelation properties. Use of magnesium chloride in tandem with gellan gum in the studied low-fat, reduced-sodium meat batters effectively compensated for the structural differences caused by fat and sodium reduction.

Synthesis of Water-Soluble 9,10-Anthraquinone Analogues with Potent Cyanobactericidal Activity toward the Musty-Odor Cyanobacterium Oscillatoria perornata

A series of water-soluble 9,10-anthraquinone analogues were prepared and evaluated for their selective toxicity toward Oscillatoria perornata, which grows in catfish production ponds and causes "musty" off-flavor in channel catfish ( Ictalurus punctatus). Water-soluble mono- and dicationic salts were prepared by conjugating various small amines directly or through a methylene or ethylene bridge to the 9,10-anthraquinone nucleus. One of the dicationic salts, 2-[ N-(1'-methyl-4'- N, N-diethylaminobutyl)aminometyl]anthraquinone diphosphate, exhibited very high water solubility and potent selective toxicity toward O. perornata. However, the tendency of this compound to potentially bind to suspended sediments may be the reason for its limitations in controlling O. perornata in catfish production ponds. The monocationic salt, 2-[ N-(1'-methylethyl)]aminomethyl]anthraquinone monophosphate, showed good solubility and high selective toxicity toward O. perornata. Neutral water-soluble analogues prepared by conjugating terta- or pentaethylene glycol directly or by a methylene bridge to the 9,10-anthraquinone nucleus had less activity than the parent compound.

Syntheses and Characterization of Unsymmetric Dicationic Salts Incorporating Imidazolium and Triazolium Functionalities

A series of both imidazolium- and triazolium-based unsymmetric dicationic salts with alkyl and polyfluoroalkyl substituents were prepared and characterized. Most of them can be classified as ionic liquids (MP < 100 degrees C). Key physical properties, such as melting point, thermal stability, density, and solubility in common solvents were determined and were compared with those of the related monocationic imidazolium- or triazolium-based salts. The effects of anions and substituents bonded to the triazolium and imidazolium cations on these properties were examined. 1-(3-Butyl-imidazolium-1-yl)methylene-(4-butyl-1,2,4-triazolium diiodide) (2d), the precursor of 1-(3-butylimidazolium-1-yl)methylene-(4-butyl-1,2,4-triazolium) bi[bis(trifluoromethanesulfonyl)amide] (3d), reacted with Pd(OAc)(2) at 120 degrees C to generate a binuclear palladium(II) dicarbene complex. The palladium(II) complex was characterized by single-crystal X-ray diffraction analysis and was used as a catalyst precursor for palladium-catalyzed Heck cross-coupling reactions in 3d. Preliminary results show that 3d could serve as both the solvent and catalyst support in the catalytic reactions.

Synthesis of 4-(Dimethylamino)pyridinium-substituted Pyrazine, Pyridazine, 1,3,5-Triazine, Purine, and Imidazole

Substitution reactions of 2,3-dichloropyrazine, 3,6-dichloropyridazine, 2,4,6-trichloro-1,3,5-triazine, 2,6-dichloropurine, and N-tosyl-2,4,5-tribromo-imidazole with 4-(dimethylamino)pyridine to monocationic, dicationic, and tricationic hetarenium salts are described.

Room-Temperature Thermotropic Ionic Liquid Crystals: Viologen Bis(Triflimide) Salts

Several dicationic salts with bis(triflimide) as counterions—otherwise known as viologens—were prepared by metathesis reaction of the corresponding viologen dibromides (diiodides) with lithium triflimide in a polar solvent. They were characterized for their thermotropic liquid-crystalline properties with various experimental techniques. Two of them had low crystal-to-smectic phase transitions (Tm) at –4 and 28°C; the other two also had low Tm values, at 51 and 58°C. Each had a wide range of LC phase. Two had relatively low crystal-to-isotropic (Tm) transitions at 117 and 131°C. Each had excellent thermal stability in the temperature range of 327–396°C. They exhibited photoluminescence property in both nonpolar and polar solvents as well as in the solid state. Their emission spectra in the solid state exhibited hypsochromic shift when compared with those in solution of dimethoxyethane.

Ambient temperature thermotropic liquid crystalline viologen bis(triflimide) salts

Two dicationic salts with bis(triflimide) as counterions exhibited crystal-to-smectic liquid crystalline phase transitions (T m=41 and 37°C) and smectic-to-isotropic liquid phase transitions (T i=112, 136°C). They had a broad liquid crystalline phase range (71–99°C) and an excellent range of thermal stability (360–364°C). Their mixtures of various compositions also displayed liquid crystalline properties from r.t. to an extended range of temperatures. They exhibited fluorescence in 1, 2-dimethoxyethane and methanol.

Formulation Protocol and Dicationic Salts Affect Protein Functionality of Model System Beef Batters

ABSTRACT: The objective of this study was to determine if addition, and order of addition, of CaCl2 and MgCl2 affected protein functionality of lean beef preblends. Four treatments were applied to non‐preblended (NPB) batters prior to thermal processing. Six treatments were applied to preblended (PB) batters 12 h prior to thermal processing. All treatments contained 2% NaCl. Dicationic salts decreased raw pH in NPB and PB batters, while cooked pH was unaffected. Magnesium chloride in NPB and CaCl2+ MgCl2 in PB batters resulted in the highest total soluble protein (TSP). Calcium chloride + MgCl2 in NPB batters resulted in firmer gels compared to the control. Magnesium chloride, in both NPB and PB, caused the greatest increase in soluble myosin, and preblending decreased myosin solubility.

Cobalt-complexed conjugated diyne salts: a family of rigid masked dielectrophiles. Syntheses, structures, and double nucleophilic substitutions.

A family of dicationic diyne salts of the general formula [(Co2(CO)6)2-mu,eta2,eta2-(Nu-CH2C(triple bond)C-C(triple bond)CCH2-Nu)][BF4]2 [Nu = SMe2 (3); Nu = NC6H7, 3-picoline, (5); Nu = NC9H7, quinoline (7)] were prepared and fully characterized. Three X-ray molecular structures of 3, 5, and the neutral starting material 2,4-hexadiyne-1,6-diol complex [(Co2(CO)6)2-mu,eta2,eta2-(HO-CH2C(triple bond)C-C(triple bond)CCH2-OH)] (1) are presented. Complex 1 crystallizes in the triclinic space group P1 with a = 14.722(2) A, b = 14.571(3) A, c = 14.722(2) A, alpha = 105.17(1) degrees, beta = 113.30(1) degrees, gamma = 99.20(1) degrees, and Z = 4. Complex 3 crystallizes in the monoclinic space group P2(1)/n with a = 12.758(3) A, b = 13.360(3) A, c = 20.494(3) A, beta = 91.44(1) degrees, and Z = 4, and compound 5 also crystallizes in the monoclinic space group P2(1)/n with a = 9.426(2) A, b = 21.739(5) A, c = 18.704(3) A, beta = 94.86(1) degrees, and Z = 4. The X-ray structures provide us with valuable information on the arrangement of the Co2-alkyne units, which have a cis geometry and are in sharp contrast to that observed generally for diyne-tetracobalt compounds. Complex [(Co2(CO)6)2-mu,eta2,eta2-(Me2S-CH2C(triple bond)C-C(triple bond)CCH2-SMe2)][BF4]2 (3) reacts with N-, S-, and P-centered nucleophiles and affords the related substituted complexes in high yields. The stability and reactivity of the disulfonium diyne complex 3 toward nucleophiles are compared to those of the analogous disulfonium-yne complex [(Co2(CO)6)2-mu,eta2,eta2-(Me2S-CH2-C(triple bond)C-CH2-SMe2)][BF4]2 (4).

2]Catenane assembly from calix[4]arene crown ethers [In Process Citation

A variety of novel calix[4]arene-incorporating crown ethers with or without intramolecular hydrogen bonding have been prepared by two efficient methods and utilized as donor rings to assemble calix[4]arene [2]catenanes based on pi-stacking interaction between hydroquinone and bipyridinium units. Treatment of calix[4]arene crown ethers 4, 10a, or 10b, whose cone conformation was fixed by intramolecular hydrogen bonding within the calix[4]arene moiety, with dicationic salt 15 x 2PF6 and dibromide 16 afforded the corresponding [2]catenanes 17a x 4PF6, 17b x 4PF6, and 17c x 4PF6 in 20%, 53%, and 55% yields, respectively, whereas from the reactions of 15 x 2PF6 and dibromide 16 in the presence of conformationally flexible 11 or 12 with a cone conformation kept by two propyl groups, [2]catenanes 18 x 4PF6 and 19 x 4PF6 were obtained in 12% and 6% yields. [2]Catenanes 21a x 4Cl, 21b x 4Cl, and 21c x 4Cl, incorporating calix[4]arene in both the donor and acceptor rings, were also successfully assembled from 10a or 10b, 16, and dicationic salts 20a x 2PF6 or 20b x 2PF6. The dynamic 1H NMR and absorption spectra of the [2]catenanes have been investigated, which revealed a strongest donor-acceptor interaction in 17a x 4PF6 and that the cone [2]catenanes 17a-c x 4PF6 can isomerize to the partial cone isomer at high temperature. The difference of the dynamic properties of these catenanes was discussed. The results demonstrate that catenation is one new general method to change the conformational distributions of calix[4]arenes.

Cationic Nickel(II) Complexes of Chelating N-Heterocyclic Carbenes

Cationic mononuclear Ni(II) complexes of the chelating N-heterocyclic carbenes tBuCCmeth and tBuCCeth (where tBuCCmeth = 1,1‘-methylene-3,3‘-di-tert-butyldiimidazole-2,2‘-diylidene (1) and tBuCCeth = 1,2-ethylene-3,3‘-di-tert-butyldiimidazole-2,2‘-diylidene (2)) have been prepared and structurally characterized. Reaction between NiCl2(PMe3)2 and 1 equiv of 1 or 2 gives the monocationic salts [(tBuCCmeth)NiCl(PMe3)]Cl (3a) and [(tBuCCeth)NiCl(PMe3)]Cl (4a), which undergo salt metathesis with TlBPh4 to give [(tBuCCmeth)NiCl(PMe3)][BPh4] (3b) and [(tBuCCeth)NiCl(PMe3)][BPh4] (4b). A comparison of the X-ray structures of 3a and 4b shows that the bite angles at the nickel atoms, 84.92(18) and 88.4(4)°, respectively, are comparable to Ni(II) complexes of two-carbon-atom bridging chelating bis-phosphines. Reaction between NiCl2(PMe3)2 or NiBr2(DME) and 2 equiv of 1 gives the Ni(II) dicationic salts [Ni(tBuCCmeth)2][X]2 (X = Cl- (5a), X = Br- (5b)). The X-ray structure of 5b reveals a square-planar geometry at th...

Self-Assembling Calix[4]arene [2]Catenanes. Preorganization, Conformation, Selectivity, and Efficiency

A novel class of preorganized U-shape calix[4]arene clefts, dicationic salts 3a,c,e.2Cl, 3b.2PF(6)(), and 3f.2Br, consisting of one cone calix[4]arene and two bipyridine residues being linked by an aliphatic chain, have been designed and synthesized as precursors for self-assembly of calix[4]arene [2]catenanes by utilizing pi-stacking interactions between the hydroquinone and bipyridinium units. Conformationally flexible 6.2PF(6)() and cone 10.2Cl, whose conformation is fixed by two propyloxy groups on the lower rim, were also prepared in order to explore the effects of conformation and hydrogen bonding of the calix[4]arene moiety on self-assembly. For all reactions, bis-p-phenylene-34-crown ether-10 (11) was employed as the donor component. Alternate cone [2]catenane 13.4Cl is obtained in 8% yield from reaction of ethylene-incorporating 3a.2Cl and 1,4-bis(bromomethyl)benzene (12a). Three cone and one conformationally flexible [2]catenanes were obtained in moderate to good yields from reactions of propylene-incorporating 3b.PF(6)() and 3c.2Cl with 12a, 1,3-bis(bromomethyl)benzene (12b) or 4,4'-(bromomethyl)biphenyl (12c). Both cone and partial cone [2]catenanes were generated in moderate yields from butylene-incorporating 3c.2Cl with four tert-butyl groups on the calix[4]arene moiety and with 12a. In contrast, only cone [2]catenane was obtained from similar tert-butyl-free cleft 3d.2Cl. Cone and conformationally flexible [2]catenanes were obtained in moderate yields, respectively, from the reactions of 3d.2Cl and 3e.2Cl with 12c. No catenanes were isolated from reaction of phenylene-incorporating 3f.2Br or 6.2Cl, whereas reaction of 10.2Cl afforded cone [2]catenane in low yield. It was demonstrated that hydrogen bonding, which may be destroyed after catenation, within the calix[4]arene moiety is crucial for efficient self-assembly of the [2]catenanes. The dynamic (1)H NMR and absorption spectra and luminescent properties of the [2]catenanes were investigated, which reveal that incorporation of calix[4]arene into the tetracationic cyclophane reduces pi-stacking interactions between the donor and acceptor units and catenation has substantial influence on conformational distributions of the calix[4]arene moiety. The results demonstrate the versatility of calix[4]arene derivatives as building blocks in the construction of supramolecular structures.