Shielding anisotropy in tin compounds: spectroscopic studies of alkyltin cations in strong acid solutions

1985 ◽  
Vol 63 (8) ◽  
pp. 2211-2216 ◽  
Author(s):  
Thomas Birchall ◽  
Veeragathy Manivannan
Keyword(s):  
Chemical Exchange ◽  
Variable Temperature ◽  
Exchange Process ◽  
Lattice Relaxation ◽  
Strong Acid ◽  
Relaxation Mechanism ◽  
Spectroscopic Studies ◽  
Spin Lattice Relaxation ◽  
System Variable ◽  
Tin Compounds

We have observed that the 119Sn nmr spectra of dialkyltin cationic species in highly acidic solutions are strongly field dependent. Relaxation time measurements at three different magnetic fields have established that the dominant spin-lattice relaxation mechanism for these species at high magnetic field is shielding anisotropy. A comparison of T1−1 and T2−1 values indicates that at room temperature a rapid chemical exchange process is occurring. In the case of the (CH3)2Sn(SO3F)2–HSO3F system variable temperature 119Sn nmr reveals the presence of three tin species which are involved in this exchange process.

scholarly journals Study of the coordination of quinuclidine to a chiral zinc phthalocyanine dimer

2016 ◽  
Vol 20 (08n11) ◽  
pp. 1224-1232 ◽  
Author(s):  
Nelson Giménez-Agulló ◽  
Gemma Aragay ◽  
José Ramón Galán-Mascarós ◽  
Pablo Ballester
Keyword(s):  
Chemical Exchange ◽  
Variable Temperature ◽  
Exchange Process ◽  
Zinc Phthalocyanine ◽  
Hydrogen Atoms ◽  
Dimerization Constant ◽  
H Nmr ◽  
Dimerization Process ◽  
Nmr Titrations ◽  
Millimolar Concentration

We attempted the calculation of an accurate equilibrium constant for the dimerization process of enantiomerically pure Zn-1 using UV-vis dilution experiments. At millimolar concentration Zn-1 is involved in a chemical exchange process between its monomeric and dimeric state that is slow on the 1H NMR timescale. We performed variable-temperature 1H NMR experiments in CDCl3 solution to determine the dimerization constant value at different temperatures and performed a van’t Hoff plot to derive the thermodynamic parameters of the process. The calculated thermodynamic data revealed that the dimerization process is entropy-driven and enthalpically opposed. We also probed the coordination of quinuclidine, 1-azabicyclo[2.2.2]octane, 2, to the Zn-1 using UV-vis and 1H NMR titrations in CDCl3 solution. At micromolar concentration the Zn-1 exclusively exists in solution as a monomer and forms a simple 1:1, [Formula: see text], complex with quinuclidine having a stability constant of [Formula: see text]([Formula: see text]) [Formula: see text] 106 M[Formula: see text]. On the other hand, the 1H NMR titrations carried out at 298 K and at millimolar concentration showed that Zn-1 was present in solution as the dimer and formed 1:2, [Formula: see text], and 2:2, [Formula: see text] complexes by coordination to 2. In addition, the 1:1 complex, [Formula: see text] showed a reduced dimerization constant compared to the uncoordinated parent monomer Zn-1. At high quinuclidine concentration, the 1:1 complex, [Formula: see text], derived from the coordinated dimer dissociation was also detected. The 1H NMR spectra of the titrations displayed separate signals for some hydrogen atoms of the Zn-phthalocyanine in each one of the four species. Remarkably, the chemical exchange processes involving free and bound quinuclidine in the monomeric and dimeric complexes showed different kinetics on the NMR timescale.

A nuclear magnetic resonance investigation of solid tetraphosphorus trisulphide

1978 ◽  
Vol 364 (1719) ◽  
pp. 553-567 ◽  
Keyword(s):  
Phase 1 ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
Minor Role ◽  
High Resolution Spectrum ◽  
Basal Nuclei ◽  
Spin Lattice ◽  
A Minor

The 31 P n. m. r. spectrum and spin–lattice relaxation time in polycrystalline P 4 S 3 have been measured between 77 and 500 K in the range 7 to 25 MHz. In phase II the 31 P n. m. r. spectra and second moments are dominated by the anisotropic chemical shift interactions. Close to the first-order phase transition at 314 K the spectra are narrowed by reorientation of the molecules about their triad axes. This motion also generates anisotropicshift spin-lattice relaxation notable for its absence of frequency dependence. The activation energy of this motion was found to be 34 kJ mol -1 . Nuclear dipolar interactions play only a minor role. In phase 1 the molecules exhibit rapid quasi-isotropic reorientation and diffusion. The anisotropic broadening interactions are averaged out and an AB 3 high-resolution spectrum of a doublet and quartet are resolved at 420 K, well below the melting point, 446 K. In this phase the spin–rotation interaction relaxation mechanism becomes dominant. Taking advantage of the remarkable motional narrowing in this compound we report the first solid-state n. m. r. J spectrum. This spectrum, recorded at 410 K, allowed the J coupling between apical and basal nuclei in solid P 4 S 3 to be measured accurately, 70.4 ± 0.5 Hz.

Spin-Gitter-Relaxation im Triplett-Zustand von Chinoxalin in Perdeutero-Naphthalin und zwei ähnlichen Mischkristallen

1975 ◽  
Vol 30 (6-7) ◽  
pp. 754-770 ◽  
Author(s):  
U. Konzelmann ◽  
D. Kilpper ◽  
M. Schwoerer
Keyword(s):  
Triplet State ◽  
Deep Trap ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Mixed Crystals ◽  
Spin Lattice Relaxation ◽  
Relaxation Processes ◽  
Shallow Trap ◽  
Field Range ◽  
Spin Lattice

Abstract Spin Lattice Relaxation in the Triplet State of Qainoxaline in Perdeuteronaphthalene and of two Similar Mixed Crystals The spin lattice relaxation in the excited triplet state of three mixed crystals was investigated: Quinoxaline in perdeutero-naphthalene, quinoxaline in naphthalene (X-traps) and quinoxaline in durene. They differ by the depth of their traps, which are shallow (90 cm -1), very shallow (60 cm -1) and deep (6600 cm -1), respectively. In order to identify the relaxation processes and the relaxation mechanism, the experiments were performed in the large magnetic field range be-tween 0.2 T and 5.4 T. By use of a non-resonant optical method and by ESR and ODMR it could be shown that at high fields the direct process (emission of resonant phonons) is the only efficient process up to 4.2 K. At low fields Raman-processes are dominant. Thereby the spin lattice relaxation probability per unit time, w, increases with the ninth power of the temperature in the shallow trap systems and with the fifth power in the deep trap system. By the analysis of the very strong anisotropy of w it could be shown that the efficient relaxation mechanism in the shallow trap systems is a guest-host-interaction modulated by phonons.

Nuclear magnetic resonance spin–lattice relaxation and the rotation of adamantane and hexamethylenetetramine in solution

1977 ◽  
Vol 55 (13) ◽  
pp. 2564-2569 ◽  
Author(s):  
Roderick E. Wasylishen ◽  
Brian A. Pettitt
Keyword(s):  
Variable Temperature ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Hard Sphere Model ◽  
Correlation Times ◽  
Spin Lattice ◽  
H Nmr ◽  
Large Step ◽  
Resonance Spin

Deuterium nmr spin–lattice relaxation times have been measured for dilute solutions of adamantane-d16 in CH2I2, CHBr3, CCl4, CHCl3, and CH2Cl2. The reorientation correlation times, τ2, calculated from the experimental data are used to calculate τJ, the angular momentum correlation times, assuming both the J-diffusion and Hubbard relations. The derived τJ values suggest that adamantane executes small step diffusion in CH2I2 and CHBr3, and large step diffusion in CCl4, CHCl3, and CH2Cl2. The calculated τJ values do not appear to be related to the mean times between collisions calculated using a hard sphere model. Both variable solvent and variable temperature experiments indicate 1 ps/cP for the viscosity dependence of the adamantane reorientation time, about 1/36th the value predicted using the familiar Stokes–Einstein equation.Carbon-13 and 1H nmr T1 data indicate that reorientation of hexamethylenetetramine in H2O (28 ps/cP), CHCl3 (27 ps/cP), and CHBr3 (18 ps/cP) is severely hindered because of inter-molecular hydrogen bonding.

1HNMR Study on the Motion of NH4+ in Ferroelectric NH4H(ClH2CCOO)2 and Mixed (NH4)1-xRbxH(ClH2CCOO)2 (x = 0.15)

2002 ◽  
Vol 57 (11) ◽  
pp. 883-887 ◽  
Author(s):  
M. Zdanowska-Fra̡czek ◽  
A. Kozaka ◽  
R. Jakubasb ◽  
J. Wa̡sickia ◽  
R. Utrechta
Keyword(s):  
Relaxation Time ◽  
Group Dynamics ◽  
Nmr Relaxation ◽  
Activation Parameters ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
Temperature Dependent ◽  
Spin Lattice

Temperature-dependent proton NMR relaxation time measurements have been performed at 60 MHz in order to study the NH4+ dynamics in ferroelectric NH4H(ClH2CCOO)2 and mixed Rbx(NH4)1-x(ClH2CCOO)2, where x = 0.15. The data indicate that the dominant relaxation mechanism for the NMR spin-lattice relaxation time T 1 in both crystals involves simultaneous NH4 group reorientation about their C2 and C3 symmetry axis in the paraelectric phase. Details of the NH4+reorientation have been inferred from analysis of temperature dependence of T1 assuming the Watton model. The activation parameters of the motionshave been determined.It has been found that the substitution of Rb does not change the activation parameters of the NH4 group dynamics.

Chlorine Nuclear Quadrupole Relaxation due to the Motion of Pyridinium Cations in Pyridinium Hexachlorometallates(IV): (pyH)2 MCl6 (M = Sn, Pb, Te)

1990 ◽  
Vol 45 (3-4) ◽  
pp. 477-480 ◽  
Author(s):  
Yutaka Tai ◽  
Tetsuo Asaji ◽  
Daiyu Nakamura
Keyword(s):  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
Reorientational Motion ◽  
Quadrupole Relaxation ◽  
Potential Wells ◽  
Spin Lattice ◽  
Pyridinium Cations ◽  
Nuclear Quadrupole Relaxation

Abstract The temperature dependence of the chlorine quadrupole spin-lattice relaxation time T1Q was observed for one of the three 35Cl NQR lines of (pyH)2 MCl6(M = Sn, Pb, Te). Each T1Q curve can be devided into three temperature regions. In the low-and high-temperature regions, T1Q is dominantly determined by the relaxation mechanism due to the libration and reorientation of [MCl6]2- , respectively. In the intermediate temperature region, T1Q results from the modulation of the electric field gradient by the motion of the neighboring pyridinium cations. This way the reorientational motion of the cation between potential wells with nonequivalent depths is precisely characterized.

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