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1.
Solid-state cross-polarization magic-angle spinning (CP/MAS) NMR spectra were recorded for the compounds [Ag(NH3)2]2SO4, [Ag(NH3)2]2SeO4 and [Ag(NH3))]NO3, all of which contain the linear or nearly linear two-coordinate [Ag(NH3)2]+ ion. The 109Ag CP/MAS NMR spectra show centrebands and associated spinning sideband manifolds typical for systems with moderately large shielding anisotropy, and splittings due to indirect 1J(109Ag,14N) spin-spin coupling. Spinning sideband analysis was used to determine the 109Ag shielding anisotropy and asymmetry parameters Deltasigma and eta from these spectra, yielding anisotropies in the range 1500-1600 ppm and asymmetry parameters in the range 0-0.3. Spectra were also recorded for 15N and (for the selenate) 77Se. In all cases the number of resonances observed is as expected for the crystallographic asymmetric units. The crystal structure of the selenate is reported for the first time. One-bond (107, 109Ag,15N) coupling constants are found to have magnitudes in the range 60-65 Hz. Density functional calculations of the Ag shielding tensor for model systems yield results that are in good agreement with the experimentally determined shielding parameters, and suggest that in the solid compounds Deltasigma and eta are reduced and increased, respectively, from the values calculated for the free [Ag(NH3)2]+ ion (1920 ppm and 0, respectively), primarily as a result of cation-cation interactions, for which there is evidence from the presence of metal-over-metal stacks of [Ag(NH3)2]+ ions in the solid-state structures of these compounds.  相似文献   

2.
Silver-containing layered networks of the form [Ag(L)] (L = 4-pyridinesulfonate or p-toluenesulfonate) were treated with primary amines in different ratios. The structures of the parent supramolecular networks are well-known; however, their interactions with primary amines lead to the formation of new layered materials for which single-crystal X-ray structures cannot be obtained. Solid-state (109)Ag, (15)N, and (13)C cross-polarization magic-angle spinning (CP/MAS) NMR experiments, in combination with powder X-ray diffraction experiments and ab initio calculations, are utilized to investigate the interactions between the primary amines and the parent materials, and to propose structural models for the new materials. (109)Ag chemical shift (CS) tensor parameters are extremely sensitive to changes in silver environments; hence, (1)H-(109)Ag CP/MAS NMR experiments are used to distinguish and characterize silver sites. The combination of (109)Ag and (15)N NMR experiments on starting materials and samples prepared with both (15)N-labeled and unlabeled amines permits the accurate measurements of indirect (1)J((109)Ag,(15)N) and (1)J((109)Ag,(14)N) spin-spin coupling constants, providing further information on structure and bonding in these systems. First principles calculations of silver CS tensors and (1)J((109)Ag,(14)N) coupling constants in model complexes aid in formulating the proposed structural models for the new materials, which are largely comprised of layers of silver-diamine cations.  相似文献   

3.
Poly(dicarbon monofluoride) (C2F)n was studied by electron paramagnetic resonance (EPR) and solid-state nuclear magnetic resonance (NMR). The effects of physisorbed oxygen on the EPR and NMR relaxation were underlined and extrapolated to poly(carbon monofluoride) (CF)n and semi-covalent graphite fluoride prepared at room temperature. Physisorbed oxygen molecules are shown to be an important mechanism of both electronic and nuclear relaxations, resulting in apparent spin-lattice relaxation time and line width during NMR and EPR measurements, respectively. The effect of paramagnetic centers on the 19F spin-lattice relaxation was underlined in accordance with the high electron spin density determined by EPR. 19F magic angle spinning (MAS) NMR, 13C MAS NMR, and 13C MAS NMR with 19F to 13C cross polarization (CP) underline the presence of two types of carbon atoms, both sp3 hybridized: some covalently bonded to fluorine and the others linked exclusively to carbon atoms. Finally, a C-F bond length of 0.138 +/- 0.002 nm has been determined thanks to the re-introduction of dipolar coupling using cross polarization.  相似文献   

4.
Two water-soluble, silver(I) complexes showing a wide spectrum of effective antibacterial and antifungal activities, i.e., ([Ag(Hhis)].0.2EtOH)2 (1; H2his = L-histidine) and [Ag(Hpyrrld)]2 (3; H2pyrrld = (S)-(-)-2-pyrrolidone-5-carboxylic acid) were prepared. In aqueous solution 1 and 3 were present as dimers, whereas in the solid state they were polymers. Crystallization of 1 by slow evaporation and/or vapor diffusion gave water-insoluble crystals of [Ag(Hhis)]n (2) showing modest antimicrobial activities. The complex 1 in the solid state is a polymer formed by intermolecular hydrogen-bonding interactions between dimeric [Ag(Hhis)]2 cores, while 2 is a different polymer without a core complex. X-ray crystallography revealed that 2 was a left-handed helical polymer consisting of a bent, 2-coordinate silver(I) atom bonding to the Namino atom of one Hhis- ligand and the N pi atom of a different Hhis- ligand. Of particular note is the fact that Ocarboxyl atoms do not participate in the coordination. X-ray crystallography also revealed that 3 was a left-handed helical polymer formed by self-assembly of dimeric [Ag(Hpyrrld)]2 cores with an intramolecular metal(I)-metal(I) interaction (Ag-Ag distance, 2.9022(7) A). The FT-IR and the solid-state 13C and 15N NMR spectra showed that the dimeric core of 1 was formed through Ag-N bonds, while that of 3 was formed through Ag-O bonds. The molecular ions of 1 and 3 were detected by the positive-ion electrospray ionization (ESI) mass spectrometry. For 1-3, characterization by elemental analysis, TG/DTA, FT-IR, and variable-temperature solid-state 13C NMR and room-temperature 15N NMR measurements was performed, and for 1 and 3, that by solution molecular weight measurements and solution (109Ag, 1H, and 13C) NMR spectroscopies was also carried out. The antibacterial and antifungal activities of 1 and 3 were remarkable and comparable to those of the previous silver(I)-N-heterocycle complexes.  相似文献   

5.
Wu G  Wasylishen RE 《Inorganic chemistry》1996,35(11):3113-3116
The first observations of (31)P-(31)P indirect spin-spin (J) coupling in copper(I) phosphine complexes are reported for solid Cu(PPh(3))(2)X (X = NO(3)(-), BH(4)(-)). Values of (2)J((31)P,(31)P), 157 +/- 5 and 140 +/- 5 Hz for Cu(PPh(3))(2)NO(3) and Cu(PPh(3))(2)BH(4), respectively, have been obtained from two-dimensional (2D) J-resolved (31)P NMR spectra obtained under slow magic-angle spinning (MAS) conditions. In both complexes, the two phosphine ligands are crystallographically equivalent; thus, the two (31)P nuclei have identical isotropic chemical shifts. Under rapid sample spinning conditions, the (31)P MAS NMR spectra exhibit relatively sharp overlapping asymmetric quartets arising from (1)J((63/65)Cu,(31)P) and residual (63/65)Cu-(31)P dipolar interactions. No evidence of (2)J((31)P,(31)P) is apparent from the spectra obtained with rapid MAS; however, under slow MAS conditions there is evidence of homonuclear J-recoupling. Peak broadening due to heteronuclear dipolar interactions precludes measurement of (2)J((31)P,(31)P) from standard 1D (31)P MAS NMR spectra. It is shown that this source of broadening can be effectively eliminated by employing the 2D J-resolved experiment. For the two copper(I) phosphine complexes investigated in this study, the peak widths in the f(1) dimension of the 2D J-resolved (31)P MAS NMR spectra are about three times narrower than those found in the corresponding 1D (31)P MAS NMR spectra.  相似文献   

6.
Lamellar structure of poly(Ala-Gly) or (AG)n in the solid was examined using 13C solid-state NMR and statistical mechanical approaches. Two doubly labeled versions, [1-13C]Gly14[1-13C]Ala15- and [1-13C]Gly18[1-13C]Ala19 of (AG)15 were examined by two-dimensional (2D) 13C spin diffusion NMR in the solid state. In addition five doubly labeled [15N,13C]-versions of the same peptide, (AG) 15 and 15 versions labeled [3-13C] in each of the successive Ala residues were utilized for REDOR and 13C CP/MAS NMR measurements, respectively. The observed spin diffusion NMR spectra were consistent with a structure containing a combination of distorted beta-turns with a large distribution of the torsion angles and antiparallel beta-sheets. The relative proportion of the distorted beta-turn form was evaluated by examination of 13C CP/MAS NMR spectra of [3-13C]Ala-(AG)15. In addition, REDOR determinations showed five kinds of atomic distances between doubly labeled 13C and 15N nuclei which were also interpreted in terms of a combination of beta-sheets and beta-turns. Our statistical mechanical analysis is in excellent agreement with our Ala Cbeta 13C CP/MAS NMR data strongly suggesting that (AG)15 has a lamellar structure.  相似文献   

7.
The sensitivity of solid-state NMR experiments can be enhanced with dynamic nuclear polarization (DNP), a technique that transfers the high Boltzmann polarization of unpaired electrons to nuclei. Signal enhancements of up to 23 have been obtained for magic angle spinning (MAS) experiments at 5 T and 85-90 K using a custom-designed high-power gyrotron. The extended stability of MAS/DNP experiments at low temperature is demonstrated with (1)H-driven (13)C spin-diffusion experiments on the amino acid proline. These (13)C-(13)C chemical shift correlation spectra are the first two-dimensional MAS/DNP experiments performed at high field (>1.4 T).  相似文献   

8.
A solid-state nuclear magnetic resonance and zeroth-order regular approximation density functional theory, ZORA-DFT, study of one-bond nuclear spin-spin coupling between group-14 nuclei and quadrupolar 35/37Cl nuclei in triphenyl group-14 chlorides, Ph3XCl (X = C, Si, Ge, Sn and Pb), is presented. This represents the first combined experimental and theoretical systematic study of spin-spin coupling involving spin-pairs containing quadrupolar nuclei. Solid-state NMR spectra have been acquired for all compounds in which X has a spin-1/2 isotope--13C, 29Si, [117/119]Sn and 207Pb-at applied magnetic fields of 4.70, 7.05 and 11.75 T. From simulations of these spectra, values describing the indirect spin-spin coupling tensor-the isotropic indirect spin-spin coupling constant, 1J(X, 35/37Cl)iso and the anisotropy of the J tensor, Delta1J(X, 35/37Cl)--have been determined for all but the lead-chlorine spin-pair. To better compare the indirect spin-spin coupling parameters between spin-pairs, 1J(iso) and Delta1J values were converted to their reduced coupling constants, 1K(iso) and Delta1K. From experiment, the sign of 1K(iso) was found to be negative while the sign of Delta1K is positive for all spin-pairs investigated. The magnitude of both 1K(iso) and Delta1K was found to increase as one moves down group-14. Theoretical values of the magnitude and sign of 1K(iso) and Delta1K were obtained from ZORA-DFT calculations and are in agreement with the available experimental data. From the calculations, the Fermi-contact mechanism was determined to provide the largest contribution to 1K(iso) for all spin-pairs while spin-dipolar and paramagnetic spin-orbit mechanisms make significant contributions to the anisotropy of K. The inclusion of relativistic effects was found to influence K(Sn,Cl) and K(Pb,Cl).  相似文献   

9.
Penner GH  Li W 《Inorganic chemistry》2004,43(18):5588-5597
In this study the (109)Ag NMR spectra of the following solid inorganic silver-containing compounds were investigated: AgNO(3), AgNO(2), Ag(2)SO(4), Ag(2)SO(3), AgCO(3), Ag(3)PO(4), AgCl, AgBr, AgI, AgSO(3)CH(3), silver p-toluenesulfonate, NaAg(CN)(2), KAg(CN)(2), K(3)Ag(CN)(4), Me(4)NAgCl(2), silver diethylthiocarbamate, silver lactate, silver acetate, silver citrate, and bis[(N,N(1)-di-tert-butylformamidinato)silver(I)]. The magic angle spinning (MAS) spectra of all compounds were obtained. In some cases, when protons were available, the (1)H to (109)Ag cross-polarization (CP) technique was used to enhance the signal and shorten the experimental relaxation delay. It was possible to obtain slow MAS (or CP/MAS) or nonspinning spectra for 10 samples, allowing the determination of the principal components of the (109)Ag chemical shift (CS) tensors. The isotropic chemical shifts and the CS tensors are discussed in light of the available crystal structures. The need for an accepted standard for referencing (109)Ag chemical shifts and the use of AgSO(3)CH(3) as a CP setup sample are also discussed.  相似文献   

10.
In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.  相似文献   

11.
Berg KE  Blixt J  Glaser J 《Inorganic chemistry》1996,35(24):7074-7081
The existence of mixed complexes of the general formula Tl(CN)(m)()Cl(n)()(3)(-)(m)()(-)(n)() (m + n 相似文献   

12.
An NMR method for determining the three-dimensional structures of membrane proteins in proteoliposomes is demonstrated by determining the structure of MerFt, the 60-residue helix-loop-helix integral membrane core of the 81-residue mercury transporter MerF. The method merges elements of oriented sample (OS) solid-state NMR and magic angle spinning (MAS) solid-state NMR techniques to measure orientation restraints relative to a single external axis (the bilayer normal) from individual residues in a uniformly (13)C/(15)N labeled protein in unoriented liquid crystalline phospholipid bilayers. The method relies on the fast (>10(5) Hz) rotational diffusion of membrane proteins in bilayers to average the static chemical shift anisotropy and heteronuclear dipole-dipole coupling powder patterns to axially symmetric powder patterns with reduced frequency spans. The frequency associated with the parallel edge of such motionally averaged powder patterns is exactly the same as that measured from the single line resonance in the spectrum of a stationary sample that is macroscopically aligned parallel to the direction of the applied magnetic field. All data are collected on unoriented samples undergoing MAS. Averaging of the homonuclear (13)C/(13)C dipolar couplings, by MAS of the sample, enables the use of uniformly (13)C/(15)N labeled proteins, which provides enhanced sensitivity through direct (13)C detection as well as the use of multidimensional MAS solid-state NMR methods for resolving and assigning resonances. The unique feature of this method is the measurement of orientation restraints that enable the protein structure and orientation to be determined in unoriented proteoliposomes.  相似文献   

13.
Solid-state (17)O NMR spectroscopy is employed to characterize powdered samples of known monoclinic and orthorhombic modifications of (17)O-enriched triphenylphosphine oxide, Ph(3)PO. Precise data on the orientation-dependent (17)O electric field gradient (EFG) and chemical shift (CS) tensors are obtained for both polymorphs. While the (17)O nuclear quadrupolar coupling constants (C(Q)) are essentially identical for the two polymorphs (C(Q) = -4.59 +/- 0.01 MHz (orthorhombic); C(Q) = -4.57 +/- 0.01 MHz (monoclinic)), the spans (Omega) of the CS tensors are distinctly different (Omega = 135 +/- 3 ppm (orthorhombic); Omega = 155 +/- 5 ppm (monoclinic)). The oxygen CS tensor is discussed in terms of Ramsey's theory and the electronic structure of the phosphorus-oxygen bond. The NMR results favor the hemipolar sigma-bonded R(3)P(+)-O(-) end of the resonance structure continuum over the multiple bond representation. Indirect nuclear spin-spin (J) coupling between (31)P and (17)O is observed directly in (17)O magic-angle-spinning (MAS) NMR spectra as well as in (31)P MAS NMR spectra. Ab initio and density-functional theory calculations of the (17)O EFG, CS, and (1)J((31)P,(17)O) tensors have been performed with a variety of basis sets to complement the experimental data. This work describes an interesting spin system for which the CS, quadrupolar, J, and direct dipolar interactions all contribute significantly to the observed (17)O NMR spectra and demonstrates the wealth of information which is available from NMR studies of solid materials.  相似文献   

14.
A new organically templated gallium oxalatophosphate, (C7H20N2)0.5[Ga3(C2O4)0.5(PO4)3], has been synthesized by using a low-melting-point eutectic mixture of choline chloride and oxalic acid as a solvent and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and solid-state NMR spectroscopy. It is the first example of ionothermal synthesis of organically templated metal oxalatophosphate. The structure contains double 6-ring units of the composition Ga6(PO4)6 which are connected by oxalate ligands and P-O-Ga bonds to form a 3-D framework. The charge-compensating organic ammonium cations which are disordered over two positions are located at the intersections of two types of 8-ring channels. 1H MAS and 13C CPMAS NMR studies confirm the presence of N,N,N',N'-tetramethyl-1,3-propanediammonium cation. The 71Ga and 31P MAS NMR spectra are also consistent with the crystal structure analysis results.  相似文献   

15.
Calculated indirect NMR spin-spin coupling constants (3)J(P,C) and (2)J(P,H) were correlated with the local structure of the P-O...H-C linkage between the nucleic acid (NA) backbone phosphate and the H-C group(s) of a nucleic acid base. The calculations were carried out for selected nucleotides from the large ribosomal subunit (Ban et al. Science 2000, 289, 905) with the aim of identifying NMR parameters suitable for detection of certain noncanonical RNA structures. As calculations in the model system, dimethyl-phosphate-guanine, suggest, the calculated indirect spin-spin couplings across the linkage are sensitive to the mutual orientation and distance between the phosphate and nucleic acid base. A short distance between the nucleic acid base and phosphate group and the angles C...P-O and P...C-H smaller than 50 degrees are prerequisites for a measurable spin-spin interaction of either coupling (|J| > 1 Hz). A less favorable arrangement of the P-O...H-C motif, e.g., in nucleotides of the canonical A-RNA, results in an effective dumping of both spin-spin interactions and insignificant values of the NMR coupling constants. The present work indicates that quantum chemical calculations of the indirect spin-spin couplings across the P-O...H-C motif can help detect some rare but important backbone topologies, as seen for example in the reverse kink-turn. Measuring of (3)J(P,C) and (2)J(P,H) couplings can therefore provide critical constraints on the NA base and phosphate geometry and help to determine the structure of NAs.  相似文献   

16.
Graphite monofluoride (CF)(n) was studied by solid-state NMR. (19)F spin-lattice relaxation time T(1) and second moment measurements of the (19)F line are presented. A "chair" conformation structure is found to be compatible with the experimental data. Relaxation is shown to be mainly due to paramagnetic oxygen. The presence of a molecular motion with an activation energy of 1.685 kJ.mol(-1) (202.7 K) is also evidenced. (19)F magic angle spinning (MAS) NMR and (13)C MAS NMR with (19)F to (13)C cross-polarization allows the determination of CF and CF(2) groups. Reintroduction of dipolar coupling by cross-polarization is used for C-F bond length determination (0.138 +/- 0.001 nm).  相似文献   

17.
Substituted pyrazolopyridines are potent inhibitors of phosphodiesterases and cyclin-dependent kinases. In this study, NMR was used to investigate the potential N1-H and N2-H tautomerism of 5-substituted pyrazolo[3,4-c]pyridine derivatives. Six compounds were fully characterized by using (1)H, (13)C, and (15)N chemical shifts and indirect (1)H--(13)C and (1)H--(15)N coupling constants. The (1)H NMR spectra were measured over a broad range of temperatures. All of the compounds were shown to exist predominantly in the N1-H tautomeric form. Complementary quantum-chemical calculations of the chemical shieldings and indirect spin-spin couplings support the structural conclusions drawn.  相似文献   

18.
Template guided enzymatic synthesis of conducting polyaniline (PANI) is a one-step reaction and more importantly, it is an environmentally friendly process. Understanding of the reaction and coupling mechanism at the molecular level is of paramount significance to improve its processability and conductivity. Solid-state NMR techniques are useful to investigate molecular structures of enzymatically synthesized polyaniline (PANI). The PANI sample in three different forms i.e., (a) as-synthesized, self-doped conducting form; (b) dedoped, base form and; (c) redoped, conducting form, are investigated by solid-state 13C and 15N CP/MAS NMR techniques. Solid-state NMR data analysis shows that the structural features of enzymatically synthesized PANI are similar to that of chemically synthesized PANI. The solid-state 13C CP/MAS NMR spectrum of the base form of PANI confirmed that benzenoid-quinoid repeating units are present in the backbone of the PANI polymer chain. The poly(vinylphosphonic acid) (PVP) template provides charge compensation during the chain growth of linear polyaniline. After the completion of template-guided synthesis of PANI, it is now possible that the PVP template can be completely removed from the complex by dedoping with aqueous NH4OH. The detached PANI from the PANI-PVP complex can then be redoped to conducting form without the presence of the template. The conductivity of the PANI and PANI-PVP complex are of the same order of magnitude. The solid-state 15N CP/MAS NMR chemical shifts are sensitive to charge distribution on the nitrogens in the backbone. The solid-state 15N CP/MAS NMR spectrum of the base form of the enzymatically derived PANI sample showed the clear signature for benzenoid-quinoid repeating units in the polymer backbone.

  相似文献   

19.
Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method.  相似文献   

20.
Accurate calculations of NMR indirect nuclear spin-spin coupling constants require especially optimized basis sets and correlated wave function methods such as CCSD or SOPPA(CCSD). Both methods scale as N(6), where N is the number of orbitals, which prevents routine applications to molecules with more than 10-15 nonhydrogen atoms. We have therefore developed a modification of the SOPPA(CCSD) method in which the CCSD singles and doubles amplitudes are replaced by CC2 singles and doubles amplitudes. This new method, called SOPPA(CC2), scales only as N(5), like the original SOPPA-method. The performance of the SOPPA(CC2) method for the calculation of indirect nuclear spin-spin coupling constants is compared to SOPPA and SOPPA(CCSD) employing a set of benchmark molecules. We also investigate the basis set dependence by employing three different basis sets optimized for spin-spin coupling constants, namely the HuzIV-su4, ccJ-pVTZ, and ccJ-pVQZ basis sets. The results of the corresponding CCSD calculations are used as a theoretical reference.  相似文献   

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