The Studies On The Intramolecular And Intermolecular Weak Interaction In Substitued1-Chlorine/Hydroxyl Anthraquinone

Substituents effects can affect materials,characters of physical chemistry, biologicalchemistry and so on. The substituents which connect to benzene ring can affect the position ofelectrophilic reaction and nucleophilic reaction. In this work, the quantitative models wereused to study the topological characters of the intramolecular halogen bonding in thesubstitued1-chlorine anthraquinone;‘Atom in molecules’(AIM) and ‘Electron localizationfunction’(ELF) method are used to discuss the substituents effects on the intramolecularhydrogen bond in1-hydroxy-anthraquinone; the intermolecular weak interactions of dimer1-chlorine anthraquinone which formed from several different directions are also discussed.In this work, all the geometries were optimized and frenquency were calculated by usingthe Gaussian03program package. The topological analysis of electron density has been doneby AIM2000program, AIMALL program and our modified program GTA2010. The ELFanalysis has been done by TOPMOD program. The electrostatic potential was analysed byGaussView5.0. This thesis mainly include the following aspects:1. The intramolecular halogen bonding in substituted1-chlorine anthraquinone werestudied at the B3LYP/6-311++G (d, p) levels of theory. The topological analysis of electrondensity on the intramolecular halogen bonding was investigated based on ‘ELF’ and ‘AIM’theory. The density matrix of σ and π are separated and the bond path and molecular graph ofπ-bond are obtained, the influences of σ and π electron density on the intramolecular halogenbond were discussed. The calculated results show that both the electron density topologicalproperties of BCP and RCP can be used as the strength measure of intramolecular halogenbond. The greater the electron density of BCP and RCP, the farther the distance between BCPand RCP, the stronger of intramolecular halogen bond is. Except the σ electron density, πelectron density also has an obvious effect on the properties of intramolecular halogen bond.2. The substituent effects on the intramolecular hydrogen bond in1-hydroxy-anthraquinone were investigated within the framework of the ‘AIM’ theory andusing ‘ELF’ analysis. A striking parallelism was found in the geometries, binding energies,and topological properties of the studied compounds. The electron density and the energydensity at the bond critical point of the weak bond, the delocalization index (DI) andintegrated properties on interatomic surface (δ(O, H)) can be used as the strength measures ofintramolecular hydrogen bond. Both the topological analysis of the electron density and theNatural Bond Orbital (NBO) analysis show that the intramolecular hydrogen bond in1-hydroxyl-anthraquinone belongs to partially covalent bond. 3. The geometries of planar1-chlorine anthraquinone dimer were optimized atB3LYP/6-311G(d,p). Six stable configurations have been got. The intermolecular bondsenergies were calculated with BSSE correction at MP2/6-311G(d,p) level. The nature ofintermolecular bonds in1-chlorine anthraquinone dimer were discussed. The calculatedresults indicate that the intermolecular bonds strength in parallel configurations are weakerthan T-shape configurations. The intermolecular bonds in1-chlorine anthraquinone dimer areall weak interactions with electrostatic properties. The total electrostatic values changes ofthe electron-acceptors could be used as the measure of intermolecular bond strength.The innovations in this thesis:1. The modified program GTA-2010has been used to deal with density matrix, σ and πelectron density are separated. The π-bond path and molecular graph are obtained. Theinfluences of σ and π electron density on the intramolecular halogen bond were discussed.2. The electron density and the energy density at the bond critical point of intramolecularhydrogen bond, the delocalization index (DI) and integrated properties on interatomic surface(δ(O, H)) can be used as the strength measures of intramolecular weak bond.3. The total electrostatic values changes of the electron-acceptors could be used as themeasure of intermolecular bond strength.