Chloroform encapsulated in p-tert-butylcalix[4]arene: Structure and dynamics
Literature Information
A complex of p-tert-butylcalix[4]arene and chloroform has been prepared and characterized in the solid state using, for the first time for any calixarene complex, the Rietveld powder XRD method, as well as variable-temperature 2H and 13C solid-state NMR. The 2H NMR spectra are composed of a central isotropic peak, attributed to a small fraction of CDCl3 in the free motion regime inside the crystal lattice, and a quadrupolar powder pattern. 2H spin–lattice relaxation times lead to activation energies for the molecular motion of 4.9±0.5 and 6.0±0.6 kJ mol−1 for the two spectral components, respectively. The temperature dependence of the static 2H spectra shows a very unusual increase in the effective quadrupolar coupling constant with temperature, caused by the change in the geometry of the complex. We show that the complexation is caused by weak dispersion interactions. The 13C MAS NMR spectrum of the guest molecule changes upon prolonged heating, while thermal analysis confirms the presence of an exothermic transition attributed to an intermediate state before the choroform is released.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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