Density Functional Theory Study of Hydrogen Bonds of Bipyridine with 1,3,5-Benzenetricarboxylic Acid

• Published in: Chinese journal of chemistry Vol. 27; no. 9; pp. 1663 - 1667
• Main Authors: Li, Quan, Zhao, Keqing
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.09.2009; WILEY‐VCH Verlag
• Subjects: 1,3,5‐benzenetricarboxylic acid; 5-benzenetricarboxylic acid; bipyridine; bipyridine, hydrogen bond; DFT; hydrogen bond
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.200990279

The hydrogen‐bonded dimer and trimer formed between 1,3,5‐benzenetricarboxylic acid and bipyridine have been investigated using a density functional theory (DFT) method and 6‐31++G** basis set. The interaction energies are −45.783 and −89.998 kJ·mol−1 for the most stable dimer and trimer, respectively, after the basis set superposition error and zero‐point corrections. The formation of O–H...N hydrogen bonds makes O–H symmetric stretching modes in the dimer and trimer red‐shifted relative to those of the 1,3,5‐benzenetricarboxylic acid monomer. The natural bond orbit analysis shows that the inter‐molecular charge transfers are 0.60475e and 1.20225e for the dimer and trimer, respectively. Thermodynamic analysis indicates that the formation of trimer is an exothermic and spontaneous process at low and room temperature. A supramolecule can be constructed through the strong N···H–O intermolecular hydrogen bonds between bipyridine and 1,3,5‐benzenetricarboxylic acid, which is in good agreement with the experimental results. Our investigation results show that the dimer and trimer formed between bipyridine and 1,3,5‐benzenetricarboxylic acid have red‐shifted hydrogen bonds O–H···N. Thermodynamic analysis indicates that the formation of trimer is an exothermic and spontaneous process at low and room temperatures. A supramolecule can be constructed through the strong N···H–O intermolecular hydrogen bonds between bipyridine and 1,3,5‐benzenetricarboxylic acid, which is in good agreement with the experimental results.