American Chemical Society
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Capturing CO2 in Quadrupolar Binding Pockets: Broadband Microwave Spectroscopy of Pyrimidine-(CO2)n, n = 1,2

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journal contribution
posted on 2024-02-02, 17:39 authored by Blair A. Welsh, Andres S. Urbina, Tuan A. Ho, Susan L. Rempe, Lyudmila V. Slipchenko, Timothy S. Zwier
Pyrimidine has two in-plane CH­(δ+)/(δ−)/CH­(δ+) binding sites that are complementary to the (δ−/2δ+/δ−) quadrupole moment of CO2. We recorded broadband microwave spectra over the 7.5–17.5 GHz range for pyrimidine-(CO2)n with n = 1 and 2 formed in a supersonic expansion. Based on fits of the rotational transitions, including nuclear hyperfine splitting due to the two 14N nuclei, we have assigned 313 hyperfine components across 105 rotational transitions for the n = 1 complex and 208 hyperfine components across 105 rotational transitions for the n = 2 complex. The pyrimidine-CO2 complex is planar, with CO2 occupying one of the quadrupolar binding sites, forming a structure in which the CO2 is stabilized in the plane by interactions with the C–H hydrogens adjacent to the nitrogen atom. This structure is closely analogous to that of the pyridine-CO2 complex studied previously by (Doran, J. L.J. Mol. Struct. 2012, 1019, 191–195). The fit to the n = 2 cluster gives rotational constants consistent with a planar cluster of C2v symmetry in which the second CO2 molecule binds in the second quadrupolar binding pocket on the opposite side of the ring. The calculated total binding energy in pyrimidine-CO2 is −13.7 kJ mol–1, including corrections for basis set superposition error and zero-point energy, at the CCSD­(T)/ 6-311++G­(3df,2p) level, while that in pyrimidine-(CO2)2 is almost exactly double that size, indicating little interaction between the two CO2 molecules in the two binding sites. The enthalpy, entropy, and free energy of binding are also calculated at 300 K within the harmonic oscillator/rigid-rotor model. This model is shown to lack quantitative accuracy when it is applied to the formation of weakly bound complexes.