Proton-Bound Dimers Of Nitrogen Heterocyclic Molecules: Substituent Effects On The Structures And Binding Energies Of Homodimers Of Diazine, Triazine, And Fluoropyridine

The bonding energies of proton-bound homodimers BH+B were measured by ion mobility equilibrium studies and calculated at the DFT B3LYP/6-311++ G** level, for a series of nitrogen heterocyclic molecules (B) with electron-withdrawing in-ring N and on-ring F substituents. The binding energies (H. dissoc) of the proton- bound dimers ( BH+B) vary significantly, from 29.7 to 18.1 kcal/mol, decreasing linearly with decreasing the proton affinity of the monomer (B). This trend differs significantly from the constant binding energies of most homodimers of other organic nitrogen and oxygen bases. The experimentally measured H. dissoc for ( 1,3-diazine) 2H+, i. e., ( pyrimidine) 2H+ and (3- F-pyridine) 2H+ are 22.7 and 23.0 kcal/ mol, respectively. The measured H. dissoc for the pyrimidine u +(3- F- pyridine) radical cation dimer (19.2 kcal/ mol) is signifcantly lower than that of the proton-bound homodimers of pyrimidine and 3-F-pyridine, reflecting the stronger interaction in the ionic H-bond of the protonated dimers. The calculated binding energies for (1,2-diazine) 2H+, (pyridine) 2H+, (2- F- pyridine) 2H+, (3- F- pyridine) 2H+, (2,6- diF- pyridine) 2H+, (4- F- pyridine) 2H+, (1,3- diazine) 2H+, ( 1,4- diazine) 2H+, (1,3,5- triazine) 2H+, and ( pentafluoropyridine) 2H+are 29.7, 24.9, 24.8, 23.3, 23.2, 23.0, 22.4, 21.9, 19.3, and 18.1 kcal/ mol, respectively. The electron- withdrawing substituents form internal dipoles whose electrostatic interactions contribute to both the decreased proton affinities of (B) and the decreased binding energies of the protonated dimers BH+ B. The bonding energies also vary with rotation about the hydrogen bond, and they decrease in rotamers where the internal dipoles of the components are aligned efficiently for inter- ring repulsion. For compounds substituted at the 3 or 4 ( meta or para) positions, the lowest energy rotamers are T- shaped with the planes of the two rings rotated by 90. about the hydrogen bond, while the planar rotamers are weakened by repulsion between the ortho hydrogen atoms of the two rings. Conversely, in ortho- substituted (1,2- diazine) 2H+ and (2- F-pyridine) 2H+, attractive interactions between the ortho ( C- H) hydrogen atoms of one ring and the electronegative ortho atoms (N or F) of the other ring are stabilizing, and increase the protonated dimer binding energies by up to 4 kcal/ mol. In all of the dimers, rotation about the hydrogen bond can involve a 2-4 kcal/ mol barrier due to the relative energies of the rotamers. (c) 2014 AIP Publishing LLC.