Theoretical study of intermolecular interactions in meso-tetraphenylporphyrin diacid dimer (H4TPPCl2)2

Abstract

The intermolecular interactions between two meso-tetraphenylporphyrin diacid H(4)TPPCl(2) monomers are investigated by density functional theory with the PBE1PBE functional and 6-31G* basis set. Structures of five stable isomers of (H(4)TPPCl(2))(2) are determined. It is found that the interaction (IMHB-1) of Cl with ortho H atoms in two phenyl groups of H(4)TPPCl(2) is unique in that it is the strongest interaction between two H(4)TPPCl(2) monomers. Natural bond orbital analysis is carried out to explain the subtle differences of hydrogen bondings in these isomers. To understand the interactions of water molecule with H(4)TPPCl(2) and (H(4)TPPCl(2))(2), structures of H(4)TPPCl(2) x H(2)O and nine isomers of (H(4)TPPCl(2))(2) x H(2)O are also determined. The binding energy of H(4)TPPCl(2) x H(2)O is 36.47 kJ mol(-1), less than that of the most stable structure of (H(4)TPPCl(2))(2) dimers, 41.59 kJ mol(-1). The dimers containing the special IMHB-1 interactions may be the elementary building blocks for the aggregation of H(4)TPPCl(2), which is supported by the crystal structure of H(4)TPPCl(2).H(2)O x 2CH(3)CN. Thus, study of the interactions between two or a small number of gas molecules can provide important information for understanding the main interactions and stable structures in related condensed-phase systems.

Density functional theory study of electronic absorption spectra and intermolecular interactions of porphyrin–borate complexes

“…The obtained geometries of the monomeric porphyrin diacids are consistent with those revealed by X-ray crystallography [21,22]. Properties of covalently or noncovalently linked porphyrin dimers have also been theoretically explored [23][24][25][26]. Therefore, we herein attempt to elucidate the electronic absorption spectra and the intermolecular interactions of TMPyP-borate complexes by means of DFT, in order to provide the guidance for designing porphyrin nanoparticles without the unfavorable self-aggregation.…”

“…doi:10.1016/j.theochem.2010.06.017 energies were calculated by means of Gaussian09 [28] package in supercomputing center of CAS. Considering the accuracy and convenience of DFT, B3LYP function on the basis set of 6-31G(d) level was employed for the geometry optimization of TMPyP, borates and TMPyP-borate complexes [18,[23][24][25][26]29,30]. On the basis of the optimized structures, the ground state electronic energies were calculated by B3LYP/6-31G(d,p) method.…”

Electrochemical study of the dication of porphyrins with carboxylic acids: Shift of the absorption bands compared to that of the redox potentials

“…The out-of-plane deformations of porphyrins and their influences on the electronic and NMR spectroscopy of the aromatic macrocycle have been of interest for chemists for more than two decades [1][2][3][4][5][6]. Chemical properties such as the basicity of two internal pyrrolenine nitrogen atoms, oxidation potentials of porphyrins and their metal complexes and binding affinity of the metal center to axial ligands are known to be modified by the out-of-plane deformations of the porphyrin core [3,7,8]. Therefore, the biological function of porphyrin cofactors in proteins may be influenced by the porphyrin out-of-plane distortions [9].…”

Theoretical study of electronic structure and absorption spectra of diacid and zinc species of series of meso-phenylporphyrins

“…A similar theoretical level has been recently used in studies of the hydrogen bond in porphyrin diacids [12] and electronic structure of zinc porphyrins [24]. For comparison, calculations at the PBEPBE [25] level were also carried out by using the SVP basis sets for all atoms.…”

“…Porphyrin diacids, as an important derivative, have attracted much attention in the past decades because of their marked out-ofplane distortion and novel spectral features with regard to neutral porphyrin [11][12][13][14][15]. Studies on the electronic structure and spectral variation of porphyrin diacids have been carried out by certain groups of researchers [16][17][18][19].…”