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The exploration of hydrogen bonding properties of 2, 6- and 3, 5-diethynylpyridine by IR spectroscopy

Hydrogen bonding properties of 2, 6- and 3, 5- diethynylpyridine were analyzed by exploring of their interactions with trimethylphosphate, as hydrogen bond acceptor, or phenol, as hydrogen bond donor, in tetrachloroethene C2Cl4. The employment of IR spectroscopy enabled unravelling of their interaction pattern as well as the determination of their association constants (Kc) and standard reaction enthalpies ( ). The association of diethynylpyridines with trimethylphosphate in stoichiometry 1:1 is established through ≡C- H***O hydrogen bond, accompanied by the secondary interaction between C≡C moiety and CH3 group of trimethylphosphate. In the complexes with phenol, along with the expected OH***N interaction, C≡C***HO interaction is revealed. In contrast to 2, 6-diethynylpyridine where the spatial arrangement of hydrogen bond accepting groups enables the simultaneous involvement of phenol OH group in both OH***N and OH***C≡C hydrogen bond, in the complex between phenol and 3, 5- diethynylpyridine this is not possible. It is postulated that cooperativity effects, arisen from the certain type of resonance-assisted hydrogen bonds, contribute the stability gain of the latter. Associations of diethynylpyridines with trimethylphosphate are characterized as weak (Kc ≈0.8-0.9 mol-1 dm3 ; ≈5-8 kJ mol-1), while their complexes with phenol as medium strong (Kc ≈5 mol-1 dm3 ; ≈15- 35 kJ mol-1). Experimental findings on the studied complexes are supported with the calculations conducted at B3LYP/6-311++G(d, p) level of theory in the gas phase. Two conformers of diethynylpyridine***trimethylphosphate dimers are formed via ≡C-H***O interaction, whereas dimers between phenol and diethynylpyridines are established through OH***N interaction.

infrared spectroscopy; density functional theory; hydrogen bond; diethynylpyridine

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