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Cation recognition plays a vital role in defining advanced functions of macromolecules in nature. An example of such an interaction is the action of a natural antibiotic, valinomycin, that behaves as a potassium ionophore. It encages the cation to transport it across a cell membrane and easily releases it inside the cell. Macrocyclic complexes of some crown ethers mimick alkali ion interactions with natural ionophores. We have synthesized complexes of two crown ethers namely benzo-15-crown-5 (2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecine) and dibenzo-15-crown-5 (6,7,9,10,17,18-hexahydrodibenzo[b,h][1,4,7,10,13]pentaoxacyclopentadecine with potassium halides (fluoride, chloride, bromide and iodide) in acetonitrile and characterized them by IR, UV, ESI-MS, 1H NMR and 13C NMR techniques. The effect of the anion on the stability of the complexes was observed by 1H NMR studies. The alkali metal ion is held to the oxygen donor atoms of the macrocyclic ring by ion-dipole interactions. The potential of the small ring oxacrown ethers, benzo-15-crown-5 and dibenzo-15-crown-5, to act as probes for potassium ions in dilute solutions (4.1 × 10?4 M) was investigated by recording the variation in the fluorescence spectra of benzo-15-crown-5 and dibenzo-15-crown-5 on complexation with potassium fluoride in acetonitrile and chloroform. The rigidity of the macrocyclic ring and proximity of fluorophore units affected the fluorescence intensity of the complexes.

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Trioxane and other acetals are purified by contacting with an alkali metal superoxide, then isolated in a purified form. Optionally, a phase transfer catalyst can be utilized in the purification. Recovered acetals are sufficiently pure for polymerization to high molecular weight.

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Transition metal complexes of P-rich phosphanes and silylphosphanes. XI. Formation, reactions, and structures of chromium carbonyl complexes from reactions of Li(THF)2[eta2-(tBu2P) 2P] with Cr(CO)5 ¡¤ THF and Cr(CO)4 ¡¤ NBD

Reactions of Li(THF)2[eta2-(tBu2P) 2P] 1 with Cr(CO)5¡¤ THF yield Li(THF)2Et2O[Cr(CO)4{eta2-( tBu2P)2P}eta1-Cr(CO)5] 2 and the compounds [Cr(CO)4{eta2-(tBu2P) 2PH}] 3, [Cr(CO)5{eta1-(tBu2P) 2PH}] 4, (tBu2P)2PH 5 and tBu2PH¡¤Cr(CO)5 6. The formation of 3, 4, 5 and 6 is due to byproducts coming from the synthesis of 1. 2 reacts with CH3COOH under formation of 3. After addition of 12-crown-4 1 with NBD¡¤Cr(CO)4 in THF forms Li(12-crown-4)2[Cr(CO)4-{eta2-( tBu2P)2P}] 7 (yellow crystals). 7 reacts with CH3COOH to 3 – which regenerates 7 with LiBu – with Cr(CO)5THF to compound 2, with NBD¡¤Cr(CO)4 in THF to 2 and 3 (ratio 1:1). With EtBr, 7 forms [Cr(CO)4{eta2-(tBu2P) 2PEt}] 8, and [Cr(CO)4{eta2-(tBu2P) 2PBr}] 9 with BrCH2-CH2Br. The compounds were characterized by means of 1H, 13C, 31P, 7Li NMR spectroscopy, IR spectroscopy, elementary analysis, mass spectra, and 2, 3 and 4 additionally by means of X-ray diffraction analysis. 2 crystallizes in the space group P1 with 2 formula units in the elementary cell; a = 10.137(9), b = 15.295(12), c = 15.897(14) A; alpha = 101.82(7), beta = 91.65(7), gamma = 98.99(7); 3 crystallizes in the space group P21/n with 4 molecules in the elementary unit; a = 11.914(6), b = 15.217(10), c = 14.534(10) A; alpha = 90, beta = 103.56(5), gamma = 90. 4: space group P1 with 2 molecules in the elementary unit; a = 8.844(4), b = 12.291(6), c = 14.411(7) A, alpha = 66.55(2), beta = 89.27(2), gamma = 71.44(2). Johann Ambrosius Barth 1996.

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Spectral investigation of the effect of anion on the stability of non covalent assemblies of 2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecine (benzo-15-crown-5) with sodium halides

A series of complexes of 2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecine (benzo-15-crown-5) with sodium halides was synthesized in acetonitrile. The effect of anion on the stability and spectral properties of complexes of benzo-15-crown-5 with sodium halides was investigated. The synthesis of complexes of sodium fluoride and sodium chloride are reported for the first time. Chloroform was used as solvent to study the assembly in solution state by 1H and 13C NMR techniques. Single crystal diffraction studies on the easily crystallizable bromide complex confirmed 1:1 stoichiometry of the complex. IR and Raman studies provided valuable evidence for a water molecule shared between the crown encapsulated cation and the counter ion to give a solvent shared ion pair (SSIP). The fluorescence spectra of the complexes were obtained in chloroform by excitation at 270?nm to study the effect of complexation on the fluorescent properties of benzo-15-crown-5.

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Crown-containing spironaphthoxazines and spiropyrans 3. Synthesis and investigation of the merocyanine form of crown-containing spirobenzothiazolinonaphthoxazine

A method for the synthesis of the spirobenzothiazolinonaphthoxazine, stable in the merocyanine form and containing a crown-ether fragment was developed. The complexing properties of the prepared merocyanine compound and the spectroscopic and photochromic characteristics of its complexes with alkaline earth metal cations were studied by NMR and UV spectroscopy. The results were analyzed using quantum-chemical calculations. The addition of alkaline earth metal perchlorates to a solution of a crown ether-containing merocyanine dye in MeCN results in the coordination of metal cations to two binding centers, namely, the crown-ether fragment and the merocyanine oxygen atom. This gives rise to two types of complexes, which differ substantially in their structurally. The complexation induces changes in the UV spectra and influences on the photochromic behavior of the prepared compound.

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Non-linear optical absorption of [{Ni(mnt)2}2]2- and its unique counter ion, a disodium triple-decker dication [Na2(benzo-15-crown-5)3(H2O)2] 2+

Reaction of NiCl2¡¤6H2O and Na2[mnt] (mnt=maleonitriledithiolate) in CH3OH at room temperature leads to Ni(II) dithiolato complex [Ni(mnt)2]2-. An oxidation process of [Ni(mnt)2]2- affords [{Ni(mnt)2}2]2- and yields solid crystalline product [Na2(benzo-15-crown-5)3(H2O) 2][{Ni(mnt)2}2] (1) in the presence of benzo-15-crown-5. X-ray diffraction analyses revealed that in solid state the dianions of 1 pack as columns and the counter ions are discrete disodium triple-decker dications. A non-linear absorption coefficient beta of 2.4 cm GW-1 was recorded at 1064 nm for 1 in acetonitrile solution with a concentration of 1.0¡Á10-4 mol l-1.

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On the facilitating effect of neutral macrocyclic ligands on the ion transfer across the interface between aqueous and organic solutions – Part III. Competitive facilitated ion-transfer

A theoretical equation of the reversible current-potential curves is derived for the competitive ion-transfer of two kinds of cations present in an aqueous (w) phase simultaneously facilitated by a macrocyclic ligand (L) present in an organic (o) phase. Especially, for the two limiting cases, i.e. case (A): c*Mj (j = 1, 2)?c*L and case (B): c*L?c*Mj (where c*Mj and c*L denote the bulk concentrations of cation Mj in the w-phase and of L in the o-phase, respectively), simple explicit expressions are derived and a method analyzing the facilitated waves is presented. Furthermore, the main part of the theoretical predictions obtained is verified experimentally at 25C by using the ion-transfer-polarographic method with the electrolyte dropping electrode, for the following four combinations: (i) competitive cations: protonated alanine and H+, L: benzo-18-crown-6 ether; (ii) Na+ and Li+, benzo-15-crown-5 ether; (iii) K+ and Na+, dibenzo-18-crown-6 ether; and (iv) Na+ and Ba2+, dibenzo-24-crown-8 ether.

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Ethynylpyrene Linked Benzocrown Ethers as Fluorescent Sensors for Metal Ions

Substances containing ethynylpyrenes linked to either one or four benzocrown ethers were synthesized, and their absorption and fluorescence spectroscopic responses to metal ions were assessed. Addition of metal perchlorates to solutions of these substances promotes short wavelength shifts in their absorption and fluorescence maxima and increases in their fluorescence intensities. The magnitudes of the fluorescence intensity increases are dependent on the ring size and number of the crown ether and the nature of the metal cation. Association constants for complex formation were calculated using fluorescence intensity versus concentration data. Analysis using Job’s plots showed that the substances containing one benzocrown ether moiety form 1:1 complexes with metal ions. Results of experiments employing repeated addition and removal of Mg(ClO4)2 demonstrate that the ON-OFF fluorescence response can be repeated at least three times. Results of molecular orbital calculations show that complexation with metal ions lowers the energies of both the pi and pi* levels of the ethynylpyrene moiety and that in some cases the vacant orbital on the metal becomes the LUMO of the complex. An explanation of the spectroscopic changes promoted by metal ions is proposed in terms of electrostatic repulsion and structural regulation.

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Crown-containing spironaphthoxazines and spiropyrans 3. Synthesis and investigation of the merocyanine form of crown-containing spirobenzothiazolinonaphthoxazine

A method for the synthesis of the spirobenzothiazolinonaphthoxazine, stable in the merocyanine form and containing a crown-ether fragment was developed. The complexing properties of the prepared merocyanine compound and the spectroscopic and photochromic characteristics of its complexes with alkaline earth metal cations were studied by NMR and UV spectroscopy. The results were analyzed using quantum-chemical calculations. The addition of alkaline earth metal perchlorates to a solution of a crown ether-containing merocyanine dye in MeCN results in the coordination of metal cations to two binding centers, namely, the crown-ether fragment and the merocyanine oxygen atom. This gives rise to two types of complexes, which differ substantially in their structurally. The complexation induces changes in the UV spectra and influences on the photochromic behavior of the prepared compound.

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Non-linear optical absorption of [{Ni(mnt)2}2]2- and its unique counter ion, a disodium triple-decker dication [Na2(benzo-15-crown-5)3(H2O)2] 2+

Reaction of NiCl2¡¤6H2O and Na2[mnt] (mnt=maleonitriledithiolate) in CH3OH at room temperature leads to Ni(II) dithiolato complex [Ni(mnt)2]2-. An oxidation process of [Ni(mnt)2]2- affords [{Ni(mnt)2}2]2- and yields solid crystalline product [Na2(benzo-15-crown-5)3(H2O) 2][{Ni(mnt)2}2] (1) in the presence of benzo-15-crown-5. X-ray diffraction analyses revealed that in solid state the dianions of 1 pack as columns and the counter ions are discrete disodium triple-decker dications. A non-linear absorption coefficient beta of 2.4 cm GW-1 was recorded at 1064 nm for 1 in acetonitrile solution with a concentration of 1.0¡Á10-4 mol l-1.

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