573-83-1

Usage

Purification Methods

Recrystallise it from water or 95% EtOH, and dry it at room temperature in vacuum. It is soluble in 200 parts of cold water and 4 parts of boiling water. [Beilstein 3 III 880, 3 IV 1390.] THE DRY SOLID EXPLODES WHEN STRUCK OR HEATED.

InChI:InChI=1/C6H3N3O7.K/c10-6-4(8(13)14)1-3(7(11)12)2-5(6)9(15)16;/h1-2,10H;/q;+1/p-1

Upstream product

• 56228-38-7 1-(γ-hydroxypropoxy)-2,4,6-trinitrobenzene 
• 364-44-3 picryl fluoride 
• 6973-40-6 2,4,6-trinitrophenyl phenyl ether 
• 38423-82-4 potassium trimethylstannate 
• 914-45-4 tetra-n-butylammonium picrate 
• 100-67-4 potassium phenolate 
• 606-35-9 1-methoxy-2,4,6-trinitrobenzene 
• 831-08-3 ethoxycarbonyl-phenyl-methylmercury ⁽¹⁺⁾; bromide 
• 973-17-1 bis(pentafluorophenyl)mercury(II) 
• 151-50-8 potassium cyanide 
• 7201-20-9 C₇H₆HgINO₂ 
• 587-85-9 diphenylmercury(II) 
• 4436-27-5 picryl iodide 
• 108-43-0 3-monochlorophenol 

Downstream Products

• 3137-29-9 4,4-diethyl-2-oxo-3-phenyl-morpholinium; picrate 
• 62967-61-7 Trimethyl-(2,4,6-trinitro-phenoxy)-silane 
• 82805-78-5 C₉H₂N₇O₁₀S^(1-)*K⁽¹⁺⁾ 
• 7614-96-2 picryl acetate 
• 82805-76-3 C₉H₃N₆O₈S^(1-)*K⁽¹⁺⁾ 
• 95784-26-2 potassium(1+) 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo<8.8.8>hexacosane picrate 
• 4185-53-9 picryl bromide 

Relevant academic research and scientific papers

Crystal structure, vibrational spectra, optical properties and density functional theory approach of a picrate salt based on substituted triphenylphosphinium

A new organic crystal, [BzTPP][PIC](1) ([BzTPP]+ = benzyl triphenylphosphinium, [PIC]- = picrate), has been grown by slow evaporation solution growth technique. Single crystal XRD reveals that it belongs to monoclinic system with P21/c. The two neighboring [BzTPP]+ cations from a dimer through C-H···π interaction while anions stack into a columnar structure through N?O, O?O and π···π interaction. The anions and cations form a column structure alternately in ···AC-AC-AC-AC··· sequence through C-H?O hydrogen bonds. The experimental vibrational bands (IR and Raman) have been discussed and assigned based on DFT calculations. The HOMO-LUMO energy gap explains the charge transfer interactions in the molecule. The thermal stability of the hybrid crystal was analyzed by TG-TDA-MS technique and revealed that the title crystal was stable up to 290 °C. The fluorescence spectra reveal three main emission peaks at 295, 388 and 543 nm upon excitation at 250 nm in solid state at room temperature. The energy of weak interactions in the molecule and nonlinear optical properties were studies using DFT calculations.

Buckyball-Based Spherical Display of Crown Ethers for de Novo Custom Design of Ion Transport Selectivity

Searching for membrane-active synthetic analogues that are structurally simple yet functionally comparable to natural channel proteins has been of central research interest in the past four decades, yet custom design of the ion transport selectivity still remains a grand challenge. Here we report on a suite of buckyball-based molecular balls (MBs), enabling transmembrane ion transport selectivity to be custom designable. The modularly tunable MBm-Cn (m = 4-7; n = 6-12) structures consist of a C60-fullerene core, flexible alkyl linkers Cn (i.e., C6 for n-C6H12 group), and peripherally aligned benzo-3m-crown-m ethers (i.e., m = 4 for benzo-12-crown-4) as ion-transporting units. Screening a matrix of 16 such MBs, combinatorially derived from four different crown units and four different Cn linkers, intriguingly revealed that their transport selectivity well resembles the intrinsic ion binding affinity of the respective benzo-crown units present, making custom design of the transport selectivity possible. Specifically, MB4s, containing benzo-12-crown-4 units, all are Li+-selective in transmembrane ion transport, with the most active MB4-C10 exhibiting an EC50(Li+) value of 0.13 μM (corresponding to 0.13 mol % of the lipid present) while excluding all other monovalent alkali-metal ions. Likewise, the most Na+ selective MB5-C8 and K+ selective MB6-C8 demonstrate high Na+/K+ and K+/Na+ selectivity values of 13.7 and 7.8, respectively. For selectivity to Rb+ and Cs+ ions, the most active MB7-C8 displays exceptionally high transport efficiencies, with an EC50(Rb+) value of 105 nM (0.11 mol %) and an EC50(Cs+) value of 77 nM (0.079 mol %).

Tuning the intramolecular charge transfer (ICT) process in push-pull systems: Effect of nitro groups

The intramolecular charge transfer (ICT) process in donor-acceptor systems has tremendous importance in various physical and biological systems. Three nitrophenolate salts were synthesized and studied here. The ICT and π → π? transition processes were identified in these derivatives using UV-Vis spectroscopy and theoretical calculations. It was observed that by simple substitution with nitro groups, one can generate and control the ICT process by regulating the charge distribution over the molecule. While for a monosubstitute nitro derivative, only one ICT band was observed, additional ICT processes can be generated at will by introducing a second nitro group. The intensity of this second ICT channel can be regulated with introduction of a third nitro group. Further, the association constants and solvation processes for these potassium nitrophenolate derivatives were found to be drastically dependent on the number of ICT channels present in the molecule. Theoretical studies (MEP analysis) support the experimental observations presented here. The results show that by simply introducing additional acceptor groups to the system, one can tune the ICT band efficiently in a conjugate system.

Synthesis, binding properties and theoretical studies of p-tert-butylhexahomotrioxacalix[3]arene tri(adamantyl)ketone with alkali, alkaline earth, transition, heavy metal and lanthanide cations

p-tert-Butylhexahomotrioxacalix[3]arene tri(adamantyl)ketone (1b) was synthesized for the first time. Compound 1b was obtained in a cone conformation in solution at room temperature, as established by NMR spectroscopy (1H and 13C). The binding properties of ligand 1b for alkali, alkaline earth, transition, heavy metal and lanthanide cations have been assessed by phase transfer and proton NMR titration experiments. Molecular mechanics and ab initio techniques were also employed to complement the NMR data. The results are compared to those obtained with other closely related homooxacalixarene derivatives. Although triketone 1b is a weak extractant, it shows a strong peak selectivity for Na+ and also some preference for Ag+. Proton NMR titrations indicate the formation of 1:1 complexes between 1b and the cations studied, and also that they should be located inside the cavity defined by the phenoxy and carbonyl oxygen atoms. Although the molecular mechanics results show little correlation with the NMR data, a good agreement was obtained with the ab initio models.

Self-assembled ionophores

Ionophores having the capacity spontaneously assemble in solution and composed of hydrogen bonded monomers of 5′-(t-butyl-dimethylsilyl)-2′,3′-O-isopropylidene-isoguanosine, 5′-(t-butyl-dimethylsilyl)-2′,3′-O-isopropylidene-thio-isoguanosine or 2′,3′-Di-O-acetyl-5′-(t-butyl-dimethylsilyl)-isoguanosine are used to remove 137-cesium ions (137Cs+) from nuclear waste.

Concerted mechanisms of the reactions of methyl aryl carbonates with substituted phenoxide ions

The reactions of 4-nitrophenyl, 2,4-dinitrophenyl, and 2,4,6-trinitrophenyl methyl carbonates (NPC, DNPC, and TNPC, respectively) with substituted phenoxide ions are subjected to a kinetic study in water at 25.0 °C, ionic strength 0.2 M (KCl). Production of the leaving groups (the nitro derivatives) is followed spectrophotometrically. Under excess of the phenoxide ions pseudo-first-order rate coefficients (kobsd) are found throughout. Plots of kobsd vs substituted phenoxide concentration at constant pH are linear, with the slope (kN) independent of pH. The Broensted-type plots (log kN vs pKa of the phenols) are linear with slopes β = 0.67, 0.48, and 0.52 for the phenolysis of NPC, DNPC, and TNPC, respectively. The magnitudes of these Broensted slopes are consistent with a concerted mechanism. In the particular case of the phenolysis of NPC the expected hypothetical curvature center of the Broensted plot for a stepwise mechanism should be pKa0 = 7.1 (the pKa of 4-nitrophenol). This curvature does not appear within the pKa range of the substituted phenols studied (5.3-10.3), indicating that these reactions are concerted. The phenolysis of DNPC and TNPC should also be concerted in view of the even more unstable tetrahedral intermediates that would be formed if the reactions were stepwise. The reactions of the same substrates with pyridines are stepwise, which means that substitution of a pyridine moiety in a tetrahedral intermediate by a phenoxy group destabilizes the intermediate perhaps to the point of nonexistence. The kN values for the title reactions are larger than those for the concerted phenolysis of the corresponding ethyl S-aryl thiolcarbonates. The kN values found in the present reactions are subjected to a dual regression analysis as a function of the pKa, of both the nucleophile and leaving group, the coefficients being βN = 0.5 and βig = -0.3, respectively. These coefficients are consistent with a concerted mechanism.

A study of C-F···M+ interaction: Alkali metal complexes of the fluorine-containing cage compound

The C-F···M+ interaction was investigated by employing a cage compound 1 that has four fluorobenzene units. The NMR (1H, 13C, and 19F) spectra and X-ray crystallographic analyses of 1 and its metal complexes showed clear evidence of the interaction. Short C-F···M+ distances (CF···K+, 2.755 and 2.727 A; C-F···Cs+ 2.944 and 2.954 A) were observed in the crystalline state of K+ ? 1 and Cs+ ? 1. Furthermore, the C-F bond lengths were elongated by the interaction with the metal cations. By calculating Brown's bond valence, it is shown that the contribution of the C-F unit to cation binding is comparable or greater than the ether oxygen in the crystalline state. Representative spectroscopic changes implying the C-F···M+ interaction were observed in the NMR (1H, 13C, and 19F) spectra. In particular, 133Cs-19F spin coupling (J = 54.9 Hz) was observed in the Cs+ complex.

Design and synthesis of a new class of nonmacrocyclic alkali metal host compounds

A new class of nonmacrocyclic metal ion hosts has been examined that features a polyspirocyclic framework that offers a 1,3,5-triaxial presentation of ligating centers. These compounds are easily synthesized and exploit stereoelectronic influences to preorganize the metal ion binding site. While compounds bearing oxygen substituents (X = OH, OMe) failed to show appreciable binding of alkali metals, the aminated host (X = NHBn) exhibitied strong binding with association constants (Ka) greater than 107-108 as measured by picrate extraction analysis.

Guest inclusion properties of calix[6]arene-based unimolecular cage compounds. On their high Cs+ and Ag+ selectivity and very slow metal exchange rates

The reaction of 1.3.5-tri-O-alkylated calix[6]arenes with 1,3,5- tris(bromomethyl)benzene yielded capped calix[6]arenes (2 with ten-butyl groups on the upper tim and 3 without tert-butyl groups) in unexpectedly high yields (80 - 91%). Combined studies of 2 and 3 by MM3 computation, X-ray analysis, and 1H NMR spectroscopy established that these calix[6]arenes feature a unique structure consisting of alternately-arranged three flattened mesitylene-linked phenyl units and three stand-up anisole units. Particularly, compound 2 possesses a closed ionophoric cavity: the upper hemisphere is closed by three ten-butyl groups of anisole units and the lower hemisphere is closed by a mesitylene cap and three anisole methoxy groups. The 1H NMR spectrum was scarcely changed at wide temperature range (30 ~ 130 °C), indicating that the structure is extremely rigidified. Both solvent extraction and spectroscopic studies established that this cavity shows the high selectivity toward Cs+ among alkali metal cations, the high affinity with Ag+, and the moderate affinity with RNH3+. Very surprisingly, the association-dissociation processes for 2 and cesium picrate was so slow that the rate could be followed by a conventional spectroscopic method. The thermodynamic parameters determined by kinetic studies disclosed that the major driving-force for Cs+ inclusion is the entropy term based on the desolvation.

New supramolecular hosts: Synthesis and cation binding studies of novel Troger's base-crown ether composites

A simple and straightforward synthesis of a novel class of supramolecular hosts containing the Troger's base moiety is reported. The cation binding properties of these macrocycles were investigated using Cram's picrate extraction method.