Molecular insights into the complex formation between dodecamethylcucurbit[6]uril and phenylenediamine isomers

IF 1.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Venkataramanan Natarajan Sathiyamoorthy, Ambigapathy Suvitha, Ryoji Sahara
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引用次数: 1

Abstract

The complexation behavior of diprotonated phenylenediamine isomers with decamethylene cucurbit[6]uril (Me12Q[6]) in 1:1 and 1:2 stoichiometry was investigated in vacuum and solution using density functional theory (DFT). Among the isomers, o-phenylenediamine (oPDA) forms an exclusion complex in 1:1 stoichiometry, while others form an inclusion complex. In the 1:2 stoichiometry, at least one of the guest molecule lie on the surface of the Me12Q[6] cavity. The structural reorganization was found to depend on the mode of interaction of the guest molecule. In the gas phase, the enthalpy and Gibbs free energy are negative for all the complexes demonstrating the encapsulation process is spontaneous and thermodynamically favorable. In the solution phase, the enthalpy and entropy are negative for complexes with guest molecules meta- and para-isomers of phenylenediamine. For oPDA as a guest, the enthalpy and entropy are positive indicating the complex formation to be nonspontaneous. The MESP isosurface of complexes shows a higher accumulation of charge in the 1:2 stoichiometry, which reduces their stability. AIM analysis shows the interaction between oPDA and Me12Q[6] is due to hydrogen bonding with moderate strength, while for the other isomers, interactions between the benzene group and the Me12Q[6] cavity were noticed. EDA analysis shows the larger contribution is the electrostatic attraction and it decreases with the increase in the guest ratio. The formation of inclusion complexes by mPDA and pPDA and the surface adsorption of oPDA on Me12Q[6] and the higher accumulation of positive charge during solvation in oPDA@Me12Q[6] complexes make them labile in the solution phase.

Graphical abstract

十二甲基葫芦[6]脲和苯二胺异构体之间复合物形成的分子见解
利用密度泛函理论(DFT)研究了双质子化苯二胺同分异构体与十亚甲基葫芦[6]脲(Me12Q[6])在1:1和1:2的化学计量中与真空和溶液中的络合行为。在同分异构体中,邻苯二胺(oPDA)以1:1的化学计量形成排斥络合物,而其他异构体形成包合络合物。在1:2的化学计量中,至少有一个客体分子位于Me12Q[6]腔的表面。发现结构重组依赖于客体分子的相互作用模式。在气相中,所有配合物的焓和吉布斯自由能均为负,表明包封过程是自发的,热力学有利。在溶液中,与客体分子的苯二胺的间异构体和对异构体的配合物的焓和熵为负。当oPDA为客体时,焓和熵均为正,表明络合物的形成是非自发的。配合物的MESP等值面在1:2的化学计量中表现出较高的电荷积累,这降低了配合物的稳定性。AIM分析表明,oPDA与Me12Q[6]之间的相互作用是由中等强度的氢键形成的,而其他同分异构体则是苯基与Me12Q[6]空腔之间的相互作用。EDA分析表明,静电吸引力的贡献较大,随着客体比的增加而减小。mPDA和pPDA形成的包合物以及oPDA在Me12Q上的表面吸附[6]以及oPDA@Me12Q[6]配合物溶剂化过程中较高的正电荷积累使其在溶液中不稳定。图形抽象
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来源期刊
Journal of Inclusion Phenomena and Macrocyclic Chemistry
Journal of Inclusion Phenomena and Macrocyclic Chemistry Agricultural and Biological Sciences-Food Science
CiteScore
4.10
自引率
8.70%
发文量
54
期刊介绍: The Journal of Inclusion Phenomena and Macrocyclic Chemistry is the premier interdisciplinary publication reporting on original research into all aspects of host-guest systems. Examples of specific areas of interest are: the preparation and characterization of new hosts and new host-guest systems, especially those involving macrocyclic ligands; crystallographic, spectroscopic, thermodynamic and theoretical studies; applications in chromatography and inclusion polymerization; enzyme modelling; molecular recognition and catalysis by inclusion compounds; intercalates in biological and non-biological systems, cyclodextrin complexes and their applications in the agriculture, flavoring, food and pharmaceutical industries; synthesis, characterization and applications of zeolites. The journal publishes primarily reports of original research and preliminary communications, provided the latter represent a significant advance in the understanding of inclusion science. Critical reviews dealing with recent advances in the field are a periodic feature of the journal.
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