Jaroslav Kriz

Interaction of Cesium Ions with Calix[4]arene-bis(t-octylbenzo-18-crown-6): NMR and Theoretical Study

Using (1)H, (13)C, and (133)Cs NMR spectra, it is shown that calix[4]arene-bis(t-octylbenzo-18-crown-6) (L) forms complexes with one (L·Cs(+)) and two (L·2Cs(+)) Cs(+) ions offered by cesium bis(1,2-dicarbollide) cobaltate (CsDCC) in nitrobenzene-d(5). The ions interact with all six oxygen atoms in the crown-ether ring and the π electrons of the calixarene aromatic moieties. According to extraction technique, the stability constant of the first complex is log β(nb)(L·Cs(+)) = 8.8 ± 0.1. According to (133)Cs NMR spectra, the value of the equilibrium constant of the second complex is log K(nb)((2))(L·2Cs(+)) = 6.3 ± 0.2, i.e., its stabilization constant is log β(nb)(L·2Cs(+)) = 15.1 ± 0.3. Self-diffusion measurements by (1)H pulsed-field gradient (PFG) NMR combined with density functional theory (DFT) calculations suggest that one DCC(–) ion is tightly associated with L·Cs(+), decreasing its positive charge and consequently stabilizing the second complex, L·2Cs(+). Using a saturation-transfer (133)Cs NMR technique, the correlation times τ(ex) of chemical exchange between L·Cs(+) and L·2Cs(+) as well as between L·2Cs(+) and free Cs(+) ions were determined as 33.6 and 29.2 ms, respectively.

Interaction of Hydrated Protons with Trioctylphosphine Oxide: NMR and Theoretical Study

Interaction of trioctylphosphine oxide (TOPO) with fully ionized hydrated protons (HP) was studied in acetonitrile-d(3) and nitrobenzene-d(5) using (1)H, (13)C, and (31)P NMR, PFG NMR, and magnetic relaxation, and the experimental results were confronted with high-precision ab initio DFT calculations. Relative chemical shifts of NMR signals of TOPO (0.02 mol/L) under the presence of HP in the molar ratio beta = 0-2.0 mol/mol show binding between TOPO and HP. Self-diffusion measurements using (1)H PFG NMR demonstrate that larger complexes with higher content of TOPO are generally formed at beta < 0.75. Analyzing the dependence of (31)P NMR chemical shifts on beta by the use of program LETAGROP, we obtained very good fitting for the assumed coexistence of three complexes (TOPO)(i).HP (named C(i)), where i = 1, 2, 3. The logarithms of the respective stabilization constants log K(i) were found to be 3.63, 4.67, and 7.23 in acetonitrile and 3.91, 6.04, and 7.92 in nitrobenzene. The (31)P NMR chemical shifts Deltadelta(i) corresponding to these complexes are 39.35, 29.51, and 19.72 ppm in acetonitrile and 38.37, 28.47, and 18.63 ppm in nitrobenzene. These values and the calculated values of alpha(i) =[C(i)]/[TOPO](0) were utilized in the analysis of the system dynamics. This was done by measuring the transverse (31)P NMR relaxation by the CPMG sequence with varying delays t(p) between the pi pulses in the mixtures with beta = 0.5, 1.25, and 1.5. Calculating the probabilities of imaginable exchange processes shows that only three of them can have significant influence on relaxation rate R(2), namely C(1) <--> TOPO, C(2) <--> C(1), and C(3) <--> C(2). Using the slopes of the R(2)-t(p)(-1) dependences in the above three mixtures, the following correlation times were obtained: tau(10) = 2.5 x 10(-6), tau(21) = 7.4 x 10(-5), tau(32) = 11.3 x 10(-5) s. The DFT calculations support the hypothesis that complexes C(1) to C(3) are the main species in the mixtures of TOPO with HP, with the only exception that additional water molecules are bound to the complexes in the case of C(1) and C(2). Schematically, the compositions of the three stable complexes is [3TOPO.H(3)O](+), [2TOPO.H(3)O.H(2)O](+), and [TOPO.H(3)O.2H(2)O](+). The relative (31)P NMR shifts calculated for the optimized structures of C(1), C(2), and C(3) are in very good agreement with the experimentally observed values.

Interaction of hydronium ion with dibenzo-18-crown-6: NMR, IR, and theoretical study.

Interaction of dibenzo-18-crown-6 (DBC) with H 3O (+) (HP) in nitrobenzene- d 5 and dichloromethane- d 2 was studied by using (1)H and (13)C NMR spectra and relaxations, FTIR spectra, and quantum chemical DFT calculations. NMR shows that the DBC*HP complex is in a dynamic equilibrium with the reactants, the equilibrium constant K being 0.66 x 10 (3), 1.16 x 10 (4), and 1.03 x 10 (4) L x mol (-1) in CD 2Cl 2, nitrobenzene, and acetonitrile, respectively. The complex appears to have a C 2 v symmetry in NMR, but FTIR combined with DFT normal mode calculations suggest that such high symmetry is only apparent and due to exchange averaging of the structure. FTIR spectra as well as energy-optimized DFT calculations show that the most stable state of the complex in solution is that with three linear hydrogen bonds of HP with one CH 2-O-CH 2 and two Ar-O-Ar oxygen atoms. The structure is similar to that found in solid state but adopts a somewhat different conformation in solution. The dynamics of exchange between bound and free DBC was studied by NMR transverse relaxation. It was found to be too fast to give reproducible results when measured with the ordinary CPMG sequence or its variant DIFTRE removing residual static dipolar interaction, but it could be established by rotating-frame measurements with high intensity of the spin-lock field. The correlation time of exchange was found to be 5.6 x 10 (-6) and 3.8 x 10 (-6) s in dichloromethane and nitrobenzene, respectively. Such fast exchange can be explained by cooperative assistance of present water molecules.

Cooperative interaction of hydronium ion with an ethereally fenced hexaarylbenzene-based receptor: an NMR and theoretical study.

Using (1)H and (13)C NMR and DFT calculations, the structure and interactions of the symmetric ethereally fenced hexaarylbenzene receptor 1 with hydronium ions were studied. Both 1 and its equimolecular complex 1.H(3)O(+) exhibit C(3v) symmetry. According to DFT, two similar optimal structures of the complex exist, the more stable one being 15.4 kJ/mol lower in energy. The equilibrium between 1 and 1.H(3)O(+) complexes is characterized by the stabilization constant K = 1.97 x 10(6) (i.e., the binding constant eta = 6.3) according to both proton and carbon NMR spectra. The exchange dynamics between 1 and the complex measured by the delay-varied CPMG sequence had to be corrected for the internal exchange processes in both 1 (conformation change) and the complex (vacillation between the two minima). After this correction, the correlation time of exchange was found to be 4.76 x 10(-5) s. Such relatively fast exchange can be explained only by it being mediated by the excess water molecules present in the system.

Protonation of Tetrapropoxy-4-tert-butylcalix[4]arene: NMR Study of Interaction and Probable Structures of the Product

Using 1H and 13C NMR spectroscopy, the interaction of tetrapropoxy-p-tert-butyl-calix[4]arene (1) with H3O+ ions produced by hydrogen bis(1,2-dicarbollyl) cobaltate (HDCC) and traces of water was studied in nitrobenzene-d 5. It was shown that 1 readily forms an equimolecular complex with H3O+. The equilibrium constant K of its formation is 2.6 at 296 K. Exchange between bound and free 1 is fast even under mild excess of HDCC, the correlation time τex being about 0.13 ms. NMR shows that H3O+ is bound to the aryl-oxygen atoms and this binding forces the calixarene cup to adopt a more open and symmetrical conformation. This conclusion is in full accord with high precision quantum DFT calculations which find one structure of the complex corresponding to a global energy minimum, in which the H3O+ ion is bound to three of the oxygen atoms by strong hydrogen bonds and to the remaining oxygen by two weaker hydrogen bonds. The calixarene part is forced into a C4 symmetrical opened form. When stored for weeks, the complex gradually transforms into other forms, most probably its hydrates, according to spectral evidence and DFT calculations.

NMR Investigation of Aniline Oligomers Produced in the Early Stages of Oxidative Polymerization of Aniline

The products obtained within early stages of the oxidative polymerization of aniline in solutions of various weak organic acids or in water, and aniline oligomers produced by the oxidation of aniline and aniline-(15)N in acetic acid (0.4 M) with a limited amount of oxidant were analyzed using 1H, 13C, and 15N 1D and 2D NMR spectroscopy and 1H PFG NMR. Such products are virtually identical in all cases, according to 1H NMR. They are always a mixture of products, among which one of them is prominent. Both native and neutralized forms of the products were examined. As shown by a combination of 1H DQF COSY, 1H NOESY, 1H-(13)C and 1H-(15)N HSQC, and 1H-(13)C and 1H-(15)N HMBC spectra, both forms of this product contain an oligoaniline moiety ended mostly by phenylamino groups. In a significant amount, the chains contain--either as an inner or terminal group--an unexpected six-member ring with an oxygen-containing substituted quinoneimine structure. The most probable structure of the major product is given. The difference between the native and neutralized forms of the product was examined. It is shown that the oligomeric chains, in particular quinoneimine units of the former one, are protonated. Both forms of the product exhibit a slight paramagnetism, and contain about 2x10(-9) mol g(-1) of unpaired electron spins.

Cooperative preassociation stages of PEO-PPO-PEO triblock copolymers: NMR and theoretical study.

Using (1)H and (13)C 1D and 2D NMR spectra, pulsed field-gradient (PFG) diffusion measurements, and (13)C relaxations supported by density functional theory (DFT) calculations, the temperature-dependent behavior of (EO)(m)(PO)(n)(EO)(m) block copolymers (m/n = 31/14, 31/72, and 17/1) in D(2)O below and at the critical micellar temperature (CMT) was investigated in order to understand the nature of primary self-association acts and their true driving force. It was shown that a conformation change of the PO block followed by mild and reversible association with other PO blocks and eventually with the inner parts of EO blocks starts at temperatures 10-12 K below the CMT. The primary process is the entropy-driven disintegration of the PPO hydration envelope based on cooperation of hydrophobic hydration and hydrogen bonding. The partial dehydration of PPO is followed by its conformation change. Both processes are cooperative and reversible with a correlation time of the order 0.01 s and an activation energy of 51.3 kJ/mol. The PPO chain in a staggered conformation is prone to self-association starting at temperatures 5-6 K below CMT. In (EO)(m)(PO)(n)(EO)(m) block copolymers, this process is complicated by the stripping of PEO chains of a part of hydrogen-bound water and entwining them with PPO. It is shown that only inner (PPO-near) parts of PEO take part in the process, the end-groups remaining free.

Hydration modes of an amphiphilic molecule: NMR, FTIR, and theoretical study of the interactions in the water-lutidine system.

Using (1)H and (13)C NMR spectra and relaxations, PFG NMR diffusion measurements, FTIR spectra, and quantum-chemical structure predictions and optimizations on the MP2/6-31G(d) level, we have studied interactions between water (W) and lutidine (2,6-dimethylpyridine, L) in a wide range of ratios. At low W content up to 35%, W was found to bind to L by an O-H***N hydrogen bond and form transient L-W aggregates containing two to four L molecules in cooperation with two to three other W molecules. At higher W content, these aggregates are gradually cleaved to single L molecules enwrapped by a hydration shell anchored in an O-H***N hydrogen bond. At all compositions of the mixture, the various hydrate forms are in fast mutual exchange with a correlation time on the order of 1 x 10(-5) s.

NMR and theoretical study of the cooperative interaction of hydrated proton with dibenzo-24-crown-8

Interaction of hydrated protons (HPs) with dibenzo‐24‐crown‐8 (DBC in nitrobenzene‐d5 was studied by 1H and 13C NMR under assistance of ab initio‐density functional theory (DFT) quantum calculations. HPs were afforded by hydrogen bis(1,2‐dicarbollyl) cobaltate (HDCC) with 3.5 M excess of H2O. The forming of a complex between HP and DBC leads to marked and additive relative shifts of both 1H and 13C signals. This was utilized for the estimation of the stabilization constant K of the complex. Its value is at least 106 l/mol, which agrees with the result of independent extraction method (logK = 6.3). Using absolute integral intensities of the HP signal in a water‐saturated system, it was shown that the form of HP present in the complex must be H5O2+, in accord with formerly published structure of the complex in crystalline form. The investigation of the dynamics of exchange between bound and free DBC by transverse relaxation using variably spaced pulses in the Carr–Purcell–Meiboom–Gill (CPMG) sequence or on‐resonance rotating‐frame relaxation with variable spin‐lock field intensity was partly hampered by the fast relaxation of some signals in the complex because of relative immobilization of its internal motions. In order to remove these effects, a pulse sequence dipolar interaction‐free transverse relaxation (DIFTRE) for static DIFTRE was devised and the MLEV17 pulse sequence with high intensity of electromagnetic field was used in a separate series of experiments. Using the results of these latter experiments, the correlation time of exchange was established to be about 0.8 ms, which complied with the shape of the spectra. The accompanying ab initio DFT calculations showed that the apparent symmetry of the molecules of both DBC and its complex with H5O2+ was probably the result of averaging of energetically close conformations (five for DBC and four for the complex). Both NMR and the calculations show that the basic mode of binding of the ion in the complex is analogous to that found in crystal but the most pronounced conformation is slightly different. Copyright