NMR-Based Structural Modeling of Graphite Oxide Using Multidimensional 13C Solid-State NMR and ab Initio Chemical Shift Calculations

Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D C-13 double-quantum/single-quantum correlation SSNMR spectrum of C-13-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf-Klinowski model (Lerf, A. et al. Phys. Chem. B 1998, 102, 4477); this model is composed of interconnected sp(2), 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. Chem. Mater. 2006, 18, 2740). C-13 chemical shift anisotropy (CSA) patterns measured by a 2D C-13 CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems

Improper Hydrogen Bonded Cyclohexane C–H ax

C-H-ax center dot center dot center dot Y-ax are a textbook prototype of steric hindrance in organic chemistry. The nature of these contacts is investigated in this work. MP2/6-31+G(d,p) calculations predicted the presence of improper hydrogen bonded C-H-ax center dot center dot center dot Y-ax of different strength in substituted cyclohexane rings. To support the theoretical predictions with experimental evidence, several synthetic 2-substituted adamantane analogues (1-24) with suitable improper H-bonded C-H-ax center dot center dot center dot Y-ax contacts of different strength were used as models of a substituted cyclohexane ring. The H-1 NMR signal separation, Delta delta(gamma-CH2), within the cyclohexane ring gamma-CH(2)s is raised when the MP2/6-31+G(d,p) calculated parameters, reflecting the strength of the H-bonded C-H-ax center dot center dot center dot Y-ax contact, are increased. In molecules with enhanced improper H-bonded contacts C-H-ax center dot center dot center dot Y-ax, like those having sterically crowded contacts (Y-ax = t-Bu) or contacts including considerable electrostatic attractions (Y-ax = O-C or O=C) the calculated DFT steric energies of the gamma-axial hydrogens are considerably reduced reflecting their electron cloud compression. The results suggest that the proton H-ax electron cloud compression, caused by the C-H-ax center dot center dot center dot Y-ax contacts, and the resulting increase in Delta delta(gamma-CH2) value can be effected not just from van der Waals spheres compression, but more generally from electrostatic attraction forces and van der Waals repulsion, both of which are improper H-bonding components

Dynamic Nuclear Polarization of Oxygen-17

Oxygen-17-detected DNP NMR of a water/glycerol glass enabled an 80-fold enhancement of signal intensity at 82 K, using the biradical TOTAPOL. The >6000-fold savings in acquisition time enable [superscript 17]O–[superscript 1]H distance measurements and heteronuclear correlation experiments. These experiments are the initial demonstration of the feasibility of DNP NMR on quadrupolar [superscript 17]O.National Institute for Biomedical Imaging and Bioengineering (U.S.) (Award EB-001960)National Institute for Biomedical Imaging and Bioengineering (U.S.) (Award EB-002804)National Institute for Biomedical Imaging and Bioengineering (U.S.) (Award EB-001035)National Institute for Biomedical Imaging and Bioengineering (U.S.) (Award EB-002026