In this work, trimethoxyboroxine (TMB) is identified as a small-molecule glass former. In its viscous liquid as well as glassy states, static and dynamic properties of TMB are explored using various techniques. It is found that, on average, the structure of the condensed TMB molecules deviates from threefold symmetry so that TMB’s electric dipole moment is nonzero, thus rendering broadband dielectric spectroscopy applicable. This method reveals the super-Arrhenius dynamics that characterizes TMB above its glass transition, which occurs at about 204 K. To extend the temperature range in which the molecular dynamics can be studied, 11B nuclear magnetic resonance experiments are additionally carried out on rotating and stationary samples: Exploiting dynamic second-order shifts, spin-relaxation times, line shape effects, as well as stimulated-echo and two-dimensional exchange spectroscopy, a coherent picture regarding the dynamics of this glass former is gained.
REFERENCES
Here, we used a density of ρ = 1.216 g/cm3.
For the simulation, we use the procedure described in detail in Ref. 29. To implement the rotation about the magic angle, the rotation angle (conventionally called γ) was incremented in steps of 2π/400. In the presence of fast dynamics, this discretization was not always sufficient; hence, an incrementation of at least 10/(νrotτ) was chosen.
Please note that a fast rotation of TMB about its threefold molecular axis would lead to an MAS spectrum characterized by an effective asymmetry parameter ηQ = 0 and to an inferior fit to the experimental 210 K spectrum in Fig. 4. For nonrotating samples, the deviations between experimental low-temperature spectra and those calculated for an effective ηQ = 0 (as well as ηCS = 0) would be particularly pronounced.
To acquire the two-dimensional spectra, a five-pulse sequence with echo delays of 10 μs (first delay) or 20 μs (second delay) was employed. We collected 229 × 8192 data points (for tm = 10 ms) or 134 × 8192 points (for tm = 0.1 ms) and coadded 128 scans. The t1 increment was 2 µs, and the t2 increment was 32 µs. After symmetrization and zero filling to 1024 × 16 384 points, a Gaussian apodization of 200 Hz was applied.
This statement does not only apply to the quadrupolarly related shifts, but, according to the references cited in Ref. 53, also in the presence of a dipolar modulation between like or unlike spins which “does not split the line but shifts it.”
Transverse relaxation is close to exponential for T > 240 K. At lower temperatures, the relaxation is more compressed, i.e., of the form in Eq. (15) with an exponent between 1 and 2, indicating that dipole-dipole interactions impact on the transverse relaxation.
From Fig. S10 of Ref. 47, it is seen that with flip angles of about 24° and ηQ ≈ 0.32 almost diagonal 2D spectra are obtained. In other words, for TMB, line shape changes corresponding to a methoxy flip are not easy to detect.