Intramolecular Dipole-dipole Interactions Research Articles

Anisotropic relaxation of nuclear spins dipolar energy of water molecules in two-dimensional nanopores - A single crystal NMR study

Energy transfer from Zeeman to dipolar order discovered by Jeener et al. is usually observed in solids with a strong dipole-dipole interaction of nuclear spins. It is not observed in liquids, where fast molecular motion completely averages this interaction. The intermediate case, when the dipole-dipole interaction of nuclear spins is only partially averaged, has been poorly studied. We report on the first measurement of an angular-dependent proton spin relaxation of a dipolar reservoir in mobile water molecules confined in the interlayer pores of a vermiculite single crystal. In this layered crystal, the intramolecular dipole-dipole interactions of nuclear spins are only partially averaged due to the restricted anisotropic molecular motion in nanopores. We show that this allows the formation of dipolar echo. We measured the spin-lattice relaxation times of the dipolar order T1D at different angles between the normal to the crystal surface and the applied magnetic field and obtained a distinct angular dependence of T1D. The minimum relaxation rate R1D was found around the magic angle of 54.74°.

A Comparative Multi-Frequency EPR Study of Dipolar Interaction in Tetra-Heme Cytochromes.

Distances between Fe ions in multiheme cytochromes are sufficiently short to make the intramolecular dipole-dipole interaction between hemes probable. In the analysis of EPR data from cytochromes, this interaction has thus far been ignored under the assumption that spectra are the simple sum of non-interacting components. Here, we use a recently developed low-frequency broadband EPR spectrometer to establish the extent of dipolar interaction in the example cytochromes, characterize its spectral signatures, and identify present limitations in the analysis. Broadband EPR spectra of Shewanella oneidensis MR-1 small tetraheme cytochrome (STC) have been collected over the frequency range of 0.45 to 13.11 GHz, and they have been compared to similar data from Desulfovibrio vulgaris Hildenborough cytochrome c3. The two cases are representative examples of two very different heme topologies and corresponding electron-transfer properties in tetraheme proteins. While in cytochrome c3, the six Fe-Fe distances can be sorted into two well-separated groups, those in STC are diffuse. Since the onset of dipolar interaction between Fe-Fe pairs is already observed in the X-band, the g values are determined in the simulation of the 13.11 GHz spectrum. Low-frequency spectra are analyzed with the inclusion of dipolar interaction based on available structural data on mutual distances and orientations between all hemes. In this procedure, all 24 possible assignments of individual heme spectra to heme topologies are sampled. The 24 configurations can be reduced to a few, but inspection falls short of a unique assignment, due to a remaining lack of understanding of the fine details of these complex spectra. In general, the EPR analysis suggests the four-heme system in c3 to be more rigid than that in STC, which is proposed to be related to different physiological roles in electron transfer.

Cross-linked polydimethylsiloxane colloid as novel contrast agent for gastrointestinal magnetic resonance imaging: Transient nuclear Overhauser effect within the interface.

With good contrast in T1 and T2 weighted imaging as well as low toxicity in 3- (4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay, this work proposes the cross-linked polydimethylsiloxane colloids as a novel non-ionic contrast agent for gastrointestinal magnetic resonance imaging. The experiments of nuclear magnetic resonance spectra and relaxation show that within the interface of the colloids, there are nuclear Overhauser effect and transient nuclear Overhauser effect (cross-relaxation). Regarding the longitudinal relaxation experiments of CH2CH2O segments of Tween 80, a two spins system is found and modeled well by the equation which is deduced based on the transient nuclear Overhauser effect proposed by Solomon. The arbitrary constant X is additionally added with the initial conditions (Iz - I0)t=0 = -2XS0 and (Sz - S0)t=0 = -2S0. For the two spins system, D1 and T1 are corresponding to longitudinal relaxation times of the bound water and the CH2CH2O respectively. Concerning the transverse relaxation experiments of the CH2CH2O, they agree with the equation with three exponential decays, defined by three relaxation times, likely corresponding to three mechanisms. These mechanisms possibly are intramolecular and intermolecular dipole-dipole (DD) interactions and scalar coupling. Within the interface, hydrogen bonding causes the positive nuclear Overhauser effect of the CH2CH2O's nuclear magnetic resonance spectra, the transient nuclear Overhauser effect of the CH2CH2O's longitudinal relaxation experiments and the intermolecular dipole-dipole interactions of the CH2CH2O's transverse relaxation experiments.

Homo- and Heterodimeric Dyes for Dye-Sensitized Solar Cells: Panchromatic Light Absorption and Modulated Open Circuit Potential.

The design of dyes for panchromatic light absorption has attracted much attention in the field of dye-sensitized solar cells (DSSCs). An approach to enhance panchromatic light absorption utilizes mixtures of complementary light-absorbing dyes as well as dyes with specific anchoring groups that facilitate interfacial charge transfer with TiO2 . Dipole-dipole interactions between the dye molecules on the surface broaden the spectrum, which results in decreased DSSC device performance. However, controlled aggregation of dyes results in broadening the spectral profile along with enhanced photocurrent generation. To control the dye-dye interaction, dimeric dyes with different dipole lengths D1 -Dsq , Dsq -Dsq were systematically designed and synthesized. The photophysical and electrochemical properties were evaluated and the EHOMO and ELUMO levels were determined; these energy levels determines the electron injection from ELUMO of the dye to ECB of TiO2 and regeneration of oxidized dye by the electrolyte, respectively. The absorption spectra of Dsq -Dsq , D1 -Dsq were broadened in solution compared to model dye Dsq ; this indicates that the dye-dye interaction is prominent in solution. In D1 -Dsq excitation energy transfer between photoexcited D1 and Dsq was explained by using Förster resonance energy transfer (FRET). The homodimeric dye showed a device performace of 2.8 % (Voc 0.607, Jsc 6.62 mA/cm2 , ff 69.3 %),whereas the heterodimeric dye D1 -Dsq showed a device performance of 3.9 % (Voc 0.652 V, Jsc 8.89 mA/cm2 , ff 68.8 %). The increased photocurrent for D1 -Dsq is due to the panchromatic IPCE response compared to Dsq -Dsq . The increased Voc is due to the effective passivation of the TiO2 surface by the spirolinker, and the effective dipole moment that shifts the conduction band on TiO2 . Hence, the open circuit potential, Voc , for the devices prepared from Dsq , D1 -Dsq and Dsq -Dsq were systematically modulated by controlling the intermolecular π-π and intramolecular dipole-dipole interactions of the dimeric dyes.

Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons

The role of internal motions and molecular geometry on 1H NMR relaxation rates in liquid-state hydrocarbons is investigated using MD (molecular dynamics) simulations of the autocorrelation functions for intramolecular and intermolecular 1H-1H dipole-dipole interactions. The effects of molecular geometry and internal motions on the functional form of the autocorrelation functions are studied by comparing symmetric molecules such as neopentane and benzene to corresponding straight-chain alkanes n-pentane and n-hexane, respectively. Comparison of rigid versus flexible molecules shows that internal motions cause the intramolecular and intermolecular correlation-times to get significantly shorter, and the corresponding relaxation rates to get significantly smaller, especially for longer-chain n-alkanes. Site-by-site simulations of 1H's across the chains indicate significant variations in correlation times and relaxation rates across the molecule, and comparison with measurements reveals insights into cross-relaxation effects. Furthermore, the simulations reveal new insights into the relative strength of intramolecular versus intermolecular relaxation as a function of internal motions, as a function of molecular geometry, and on a site-by-site basis across the chain.

On the theory of the proton dipolar-correlation effect as a method for investigation of segmental displacement in polymer melts.

A thorough theoretical description of the recently suggested method [A. Lozovoi et al. J. Chem. Phys. 144, 241101 (2016)] based on the proton NMR dipolar-correlation effect allowing for the investigation of segmental diffusion in polymer melts is presented. It is shown that the initial rise of the proton dipolar-correlation build-up function, constructed from Hahn Echo signals measured at times t and t/2, contains additive contributions from both inter- and intramolecular magnetic dipole-dipole interactions. The intermolecular contribution depends on the relative mean-squared displacement of polymer segments from different macromolecules, which provides an opportunity for an experimental study of segmental translational motions at the millisecond range that falls outside the typical range accessible by other methods, i.e., neutron scattering or NMR spin echo with the magnetic field gradients. A comparison with the other two proton NMR methods based on transverse spin relaxation phenomena, i.e., solid echo and double quantum resonance, shows that the initial rise of the build-up functions in all the discussed methods is essentially identical and differs only in numerical coefficients. In addition, it is argued that correlation functions constructed in the same manner as the dipolar-correlation build-up function can be applied for an experimental determination of a mean relaxation rate in the case of systems possessing multi-exponential magnetization decay.

Imidazolium ionic liquid induced one-step synthesis of 𝜶-Fe2O3 nanorods and nanorod assemblies for lithium-ion battery

α - Fe 2 O 3 nanorods and nanorod assemblies are prepared via a facile one-step method with the assistance of imidazolium-based ionic liquid. The aspect ratio of synthesized nanorods is determined by the alkyl chain length of [Cnmim]+. The inter-molecular π−π interaction and intra-molecular dipole-dipole interaction among imidazole rings of [C4mim]+[PhCOO]− play critical roles in both nucleation and assembly processes of α-Fe2O3 nanorods. The α-Fe2O3 nanorod assemblies show an excellent performance in lithium-ion batteries with a reversible capacity of 1007.3 mA h g−1 at the rate of 500 mA g−1 after 150 cycles.

Communication: Proton NMR dipolar-correlation effect as a method for investigating segmental diffusion in polymer melts.

A simple and fast method for the investigation of segmental diffusion in high molar mass polymer melts is presented. The method is based on a special function, called proton dipolar-correlation build-up function, which is constructed from Hahn Echo signals measured at times t and t/2. The initial rise of this function contains additive contributions from both inter- and intramolecular magnetic dipole-dipole interactions. The intermolecular contribution depends on the relative mean squared displacements (MSDs) of polymer segments from different macromolecules, while the intramolecular part reflects segmental reorientations. Separation of both contributions via isotope dilution provides access to segmental displacements in polymer melts at millisecond range, which is hardly accessible by other methods. The feasibility of the method is illustrated by investigating protonated and deuterated polybutadiene melts with molecular mass 196 000 g/mol at different temperatures. The observed exponent of the power law of the segmental MSD is close to 0.32 ± 0.03 at times when the root MSD is in between 45 Å and 75 Å, and the intermolecular proton dipole-dipole contribution to the total proton Hahn Echo NMR signal is larger than 50% and increases with time.

Proton spin dynamics in polymer melts: New perspectives for experimental investigations of polymer dynamics

The proton spin dynamics in polymer melts is determined by intramolecular and intermolecular magnetic dipole-dipole interactions among the proton spins. During many decades it was postulated that the main contribution is a result of intramolecular magnetic dipole-dipole interactions of protons belonging to the same polymer segment. This postulate is far from reality. The relative weights of intra- and intermolecular contributions are time (or frequency) dependent and sensitive to details of polymer chain dynamics. It is shown that for isotropic models of polymer dynamics, in which already at short times the segmental displacements are not correlated with the polymer chain’s initial conformation, the influence of the intermolecular dipole-dipole interactions becomes stronger with increasing evolution time (i.e. decreasing frequency) than the corresponding influence of the intramolecular counterpart. On the other hand, an inverted situation is predicted by the tube-reptation model: here the influence of the intramolecular dipole-dipole interactions increases faster with time than the contribution from intermolecular interactions. This opens a new perspective for experimental investigations of polymer dynamics by proton NMR, and first results are reported.

Acyclic tethers mimicking subunits of polysaccharide ligands: selectin antagonists.

We report on the design and synthesis of molecules having E- and P-selectins blocking activity both in vitro and in vivo. The GlcNAc component of the selectin ligand sialyl Lewis(X) was replaced by an acyclic tether that links two saccharide units. The minimization of intramolecular dipole-dipole interactions and the gauche effect would be at the origin of the conformational bias imposed by this acyclic tether. The stereoselective synthesis of these molecules, their biochemical and biological evaluations using surface plasmon resonance spectroscopy (SPR), and in vivo assays are described. Because the structure of our analogues differs from the most potent E-selectin antagonists reported, our acyclic analogues offer new opportunities for chemical diversity.

The solvent dynamics at pore surfaces in molecular gels studied by field-cycling magnetic resonance relaxometry.

The molecular dynamics of the solvent molecules at liquid-solid interfaces in low molecular mass gels and in bulk solvents have been identified and characterized with the aid of field-cycling NMR relaxometry. The gels are formed using ethylene glycol (EG) and 1,3-propanediol (PG) with different concentrations of 4,6,4',6'-O-terephthalylidene-bis(methyl α-D-glucopyranoside) (gelator 1). The spin-lattice relaxation times of bulk solvents measured in the function of Larmor frequency were analyzed assuming the intramolecular and intermolecular dipole-dipole interactions. For analysis of the relaxation data for confined solvents the two-phase fast-exchange model was assumed. It was found that in a low-frequency range a dominating NMR relaxation mechanism of solvent interacting with internal surfaces of pores in studied molecular gels is reorientation mediated by translational displacements (RMTD). This dynamic process allows us to explain a very long correlation time of the order of 10(-5) s calculated for confined EG molecules and an even longer one for PG. The RMTD contribution to the relaxation is described by power-law frequency dependence. In the 1/EG gels the exponent is equal to 0.5 for all gelator concentrations suggesting the equipartition of the diffusion modes with different wavelengths. In this gel the relaxation dispersion data were transformed to a susceptibility representation and a "master-like" curve was constructed. In the 1/PG gel the exponent varies in the function of gelator concentration. Different behavior of the relaxation dispersion shape is due to the relative sizes of the ordered (at surface) and bulk-like phase. In the 1/EG gel the surface layer of the ordered molecules is always much smaller than the dimensions of the gel cavities whereas it differs in the 1/PG gel as a consequence of the disruption of the PG aggregates due to the solvent-gelator interaction.

On the theory of the proton free induction decay and Hahn echo in polymer systems: The role of intermolecular magnetic dipole-dipole interactions and the modified Anderson–Weiss approximation

The influence of the intermolecular magnetic dipole-dipole interaction on the free induction decay (FID) as well as on the Hahn-echo of proton spins in polymer melts is investigated. It is shown that for isotropic models of polymer dynamics, when polymer segment displacements do not correlate with an initial chain conformation, the influence of the intermolecular magnetic dipole-dipole interactions to the FID and Hahn echo is increasing more rapidly with evolution time than the corresponding influence of the intramolecular magnetic dipole-dipole interactions. On the other hand, the situation is inverted for the tube-reptation model: here the influence of the intramolecular magnetic dipole-dipole interactions to the FID and Hahn echo is increasing faster with time than the contribution from intermolecular interactions. A simple expression for the relative mean squared displacements of polymer segments from different chains is obtained from the intermolecular contribution to the FID. A modified Anderson-Weiss approximation, taking into account flip-flop transitions between different spins, is proposed and on that basis, the conditions for extracting the relative intermolecular mean squared displacements of polymer segments from the intermolecular contribution to the proton FID is established. Systematic investigations of intermolecular contributions, which were considered as an unimportant factor for FID and Hahn echo in polymer systems by most previous works, actually cannot be considered as negligible and opens a new dimension for obtaining information about polymer dynamics in the millisecond regime.

A new approach to explore the binding space of polysaccharide-based ligands: selectin antagonists.

The discovery of molecules that interfere with the binding of a ligand to a receptor remains a topic of great interest in medicinal chemistry. Herein, we report that a monosaccharide unit of a polysaccharide ligand can be replaced advantageously by a conformationally locked acyclic molecular entity. A cyclic component of the selectin ligand Sialyl Lewis(x), GlcNAc, is replaced by an acyclic tether, tartaric esters, which link two saccharide units. The conformational bias of this acyclic tether originates from the minimization of intramolecular dipole-dipole interaction and the gauche effect. The evaluation of the binding of these derivatives to P-selectin was measured by surface plasmon resonance spectroscopy. The results obtained in our pilot study suggest that the discovery of tunable tethers could facilitate the exploration of the carbohydrate recognition domain of various receptors.

A 1:1 co-crystal of the herbicide triflusulfuron-methyl and its degradation product triazine amine

The herbicide triflusulfuron-methyl (systematic name: methyl 2-{[4-dimethyl­amino-6-(2,2,2-trifluoro­eth­oxy)-1,3,5-triazin-2-yl]carbamoylsulfamo­yl}-3-methyl­benzoate) and its degradation product triazine amine [systematic name: 2-amino-4-dimethyl­amino-6-(2,2,2-trifluoro­eth­oxy)-1,3,5-triazine] form a triclinic 1:1 co-crystal of the title compound, C7H10F3N5O·C17H19F3N6O6S, in which its two components are connected via a pair of complementary N—H⋯N hydrogen bonds, similar to the monoclinic crystal structure of the parent compound triflusulfuron-methyl [Mereiter (2011 ▶). Acta Cryst. E67, o1778–o1779] in which a pair of mol­ecules related by a twofold axis are linked by two N—H⋯N bonds. The triflusulfuron-methyl mol­ecules of both crystal structures are similar in geometric parameters and conformation, which is due to stiffening by a short intra­molecular N—H⋯N bond [N⋯N = 2.620 (4) Å] and an intra­molecular dipole–dipole inter­action between the sulfamide and the carboxyl moieties, with Os⋯Cc = 2.802 (5) Å and Oc⋯Ns = 2.846 (4) Å. Inter­molecular N—H⋯O hydrogen bonds and slipped π–π stacking inter­actions between the diamino­triazine moieties [perpendicular distances of 3.25 Å within hydrogen-bonded tetra­mers and 3.27 Å between adjacent tetra­mers] link the two constituents of the co-crystal into columns parallel to the a axis. An intra­molecular C—H⋯O hydrogen bond occurs in the triflusulfuron-methyl mol­ecule and inter­molecular C—H⋯O inter­actions between triflusulfuron-methyl mol­ecules occur in the crystal structure. In the triflusulfuron-methyl molecule the dihedral angle between the least-squares planes of the two rings is 75.8 (1)°. In the triazine molecule, the CF3 group is partly orientationally disordered.

The herbicide triflusulfuron-methyl

The mol­ecule of the title compound [systematic name: methyl 2-({[4-dimethyl­amino-6-(2,2,2-trifluoro­eth­oxy)-1,3,5-triazin-2-yl]carbamo­yl}sulfamo­yl)-3-methyl­benzoate], C17H19F3N6O6S, features a nearly planar (r.m.s. deviation = 0.098 Å) dimethyl­amino­triazinyl-urea group with a short intra­molecular N—H⋯N hydrogen bond to a triazine N atom. An intra­molecular dipole–dipole inter­action between the sulfamide and carboxyl­ate groups, with Os⋯Cc = 2.800 (1) Å and Ns⋯Oc = 2.835 (1) Å, controls the orientation of the methyl­benzoate group and the shape of the mol­ecule. The crystal structure is stabilized by inter­molecular N—H⋯N hydrogen bonding, C—H⋯X (X = N,O) inter­actions and arene π–π stacking.

Two-photon resonant hyperpolarizability of an H-shaped molecule studied by wavelength-tunable hyper-Rayleigh scattering

Wavelength dependent hyper-Rayleigh scattering measurements have been performed by using a fluorescence spectrometer. With this detection strategy, first molecular hyperpolarizability (β) of a dual charge-transfer (H-shaped) chromophore and its monomer have been measured in two-photon resonance range from 670 to 950 nm as well as at off-resonance of 1064 nm. The absorption and resonance hyper-Rayleigh profiles can be simulated reasonably well with a common set of parameters. In addition, both resonance and off-resonance results show that β(0) per chromophore has a remarkable enhancement for the H-shaped molecule as large as 1.7, compared with that of the monomer, which could be ascribed to two physical effects: (1) coherent enhancement of two chromophores and (2) intramolecular dipole-dipole interaction, which was confirmed by their fluorescence-decay behaviors.

NMR Studies on Effects of Temperature, Pressure, and Fluorination on Structures and Dynamics of Alcohols in Liquid and Supercritical States

We measured 1H NMR chemical shifts (delta H) and 1H and 2H NMR spin-lattice relaxation times (1H- and 2H-T1) of methanol, ethanol, 2-propanol, 2,2,2-trifluoroethanol, and 1,1,1,3,3,3-hexafluoro-2-propanol in the temperature range from 298 to 673 K at reduced pressures ( Pr = P/ Pc) of 1.22 and 3.14. The delta H values showed that the degree (X HB) of hydrogen bonding decreased in the order of methanol > ethanol >2-propanol > H2O, and that the hydrogen bonding was much affected by fluorination, because of the intramolecular H-F interactions in supercritical (sc) states. Moreover, 1H- T 1 measurements revealed that the relaxation processes of OH groups in nonfluoroalcohols are controlled by dipole-dipole (DD) and spin-rotation (SR) mechanisms below and above the critical temperature (Tc), while the cross-correlation effects connected with intramolecular DD interactions between a carbon atom and an adjacent proton played an important role for hydrocarbon groups (CHn, n = 1-3) under sc conditions. This interpretation was also supported by two other results. The first is that the intramolecular H-F interactions strongly inhibit the internal rotation of CH and CH2 groups of sc fluoroalcohols, and the second is that the molecular reorientational correlation times (tauc(D)) obtained from 2H- T 1 values of deuterated hydrocarbon groups (CDn ) at temperatures above T c have significantly less temperature dependence than those of OD groups. Actually, the apparent activation energy (DeltaEa) for molecular reorientational motions in sc alcohols was smaller compared with liquid alcohols, being about 1 order of magnitude.

Membrane-peptide interaction studied by PELDOR and CW ESR: Peptide conformations and cholesterol effect on the spatial peptide distribution in the membrane

Pulsed electron-electron double resonance (PELDOR) combined with continuous-wave electron paramagnetic resonance was used to study inter- and intramolecular dipole-dipole interactions between spin labels for spin-labeled analogs of trichogin GA IV bound to multilamellar membranes of egg L-α-phosphatidylcholine (ePC) and in ePC membranes containing cholesterol. All samples were frozen to 77 K. For mono-labeled peptide concentrations in lipid over the range between 0.5 to 2.2 mol%, it is shown that in these membranes trichogin molecules are distributed homogeneously and are likely to be located on or near the inner and outer membrane surfaces. Addition of cholesterol to a final concentration of 16.5 mol% leads to an increase of the local concentration of trichogin molecules in the membranes. For the double-labeled trichogin, a distribution of the intramolecular distance between the two spin labels was observed. The distribution function is characterized by two main maxima located at distances of 1.3 and 1.8 nm. The distance of 1.3 nm is close to that expected for the α-helix structure of the peptide chain. The distance of 1.8 nm corresponds to a mixed structure in which a 310-helix is combined with a set of even more elongated conformations.

5-Cyanoimino-4-oxomethylene-4,5-dihydroimidazole and Nitrosative Guanine Deamination. A Theoretical Study of Geometries, Electronic Structures, and N-Protonation

The 5-cyanoimino-4-oxomethylene-4,5-dihydroimidazole 1 (R = H), its N1-derivatives 2 (R = Me) and 3 (R = MOM) and their cyano-N (4, 6, 8) and imino-N protonated (5, 7, 9) derivatives were studied with RHF, B3LYP, and MP2 theory. Solvation effects were estimated with the isodensity polarized continuum model (IPCM) at the MP2 level using the dielectric constant of water. Carbodiimide 10, cyanamide 12, N-cyanomethyleneimine 13, and its protonated derivatives 14 and 15 were considered for comparison as well. Adequate theoretical treatment requires the inclusion of dispersion because of the presence of intramolecular van der Waals, charge-dipole, and dipole-dipole (including H-bonding) interactions. All conformers were considered for the MOM-substituted systems, and direct consequences on the preferred site of protonation were found. The vicinal push (oxomethylene)-pull (cyanoimino) pattern of the 5-cyanoimino-4-oxomethylene-4,5-dihydroimidazoles results in the electronic structure of aromatic imidazoles with 4-acylium and 5-cyanoamido groups. The gas-phase proton affinities of 1-3 are over 30 kcal/mol higher than that for N-cyanomethyleneimine 13, and this result provides compelling evidence in support of the zwitterionic character of 1-3. Protonation enhances the push-pull interaction; the OC charge is increased from about one-half in 1-3 to about two-thirds in the protonated systems. In the gas phase, cyano-N protonation is generally preferred but imino-N protonation can compete if the R-group contains a suitable heteroatom (hydrogen-bond acceptor, Lewis base). In polar solution, however, imino-N protonation is generally preferred. Solvation has a marked consequence on the propensity for protonation. Whereas protonation is fast and exergonic in the gas phase, it is endergonic in the polar condensed phase. It is an immediate consequence of this result that the direct observation of the cations 8 and 9 should be possible in the gas phase only.

Structure and Dynamics of a Trinuclear Gadolinium(III) Complex: The Effect of Intramolecular Electron Spin Relaxation on Its Proton Relaxivity(1).

The trinuclear [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) complex has been characterized in aqueous solution as a model compound from the point of view of MRI: the parameters that affect proton relaxivity have been determined in a combined variable temperature, pressure, and multiple-field (17)O NMR, EPR, and NMRD study. The solution structure of the complex was found to be the same as in solid state: the total coordination number of the lanthanide(III) ion is 8 with two inner-sphere water molecules. EPR measurements proved a strong intramolecular dipole-dipole interaction between Gd(III) electron spins. This mechanism dominates electron spin relaxation at high magnetic fields (B > 5 T). Its proportion to the overall relaxation decreases with decreasing magnetic field and becomes a minor term at fields used in MRI. Consequently, it cannot increase the electronic relaxation rates to such an extent that they limit proton relaxivity. [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) undergoes a relatively slow water exchange (k(ex)(298) = (1.1 +/- 0.2) x 10(7) s(-1)) compared to the Gd(III) aqua ion, while the mechanism is much more associatively activated as shown by the activation volume (DeltaV () = (-12.7 +/- 1.5) cm(3) mol(-)(1)). The lower exchange rate, as compared to [Gd(H(2)O)(8)](3+) and [Gd(PDTA)(H(2)O)(2)](-), can be explained with the higher rigidity of the [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) which considerably slows down the transition from the eight-coordinate reactant to the nine-coordinate transition state. The unexpectedly low rotational correlation time of the complex is interpreted in terms of a spherical structure with a large hydrophobic surface avoiding the formation of a substantial hydration sphere around [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+).