DFT study of zinc, cadmium, mercury, copper, silver, and gold complexes of 21,23-dioxaporphyrin and one-dimensional arrays of those complexes

Abstract

Complexes of 21,23-dioxaporphyrin with neutral Zn, Cd, Hg, Cu, Ag, and Au atoms as well as some one-dimensional arrays of those complexes containing up to ten repeat units were modeled at the PBE/def2-TZVPP level of theory with D3 empirical dispersion correction. The binding energy between the metal atom and the macrocycle was found to vary from 90 kcal/mol for Cu to -14 kcal/mol for Hg. Strong charge transfer from the metal to the macrocycle accompanied complex formation. The complexes were able to form dimers and nanoarrays that were held together mostly by dispersion forces. Different types of dimers were studied: face-to-face (F) and two types of parallel-displaced ones. F dimers were calculated to be the lowest-energy structures for Cu and Ag systems. Nanoarray formation was studied for these complexes. The band gaps (Eg) of the nanoarrays were found to be smaller than 1 eV, and decreased slightly as the number of repeat units in the nanoaggregates increased. The ionization potentials and electron affinities were greatly affected by the number of repeat units due to the delocalization of polarons over the entire nanoarray. The polaron delocalization and the related reorganization energies depended to a considerable extent on the metal present in the complex. For the studied nanoarrays, the reorganization energies for hole and electron transport decreased linearly with 1/n, where n is the number of repeat units in the nanoaggregate; for an infinitely long chain, the reorganization energy was zero for electron transport and 0.03-0.04 eV for hole transport.

Stacks of Metalloporphyrins: Comparison of Experimental and Computational Results

“…interactions between porphyrin or phthalocyanine units, and thus can lead to formation of various stacks of porphyrins/phthalocyanines. ,− It was shown that porphyrins are able to self-assemble both in solution and in the solid state, forming one-, two-, or three-dimensional structures due to coordination, hydrogen bonding, and π–π stacking. , So far, computational studies on the porphyrin–porphyrin interactions have been relatively scarce (see, e.g., refs , , , and ). Also, a few computational studies have been performed describing the electronic structures and transport properties of one-dimensional arrays of closely related phthalocyanines. − It is also necessary to mention two more recent theoretical studies of 1D-arrays/stacks formation by core-modified porphyrins: 21,23-dioxaporphyrin and completely P-substituted − porphyrin ZnP­(P) 4 …”

“…Also, a few computational studies have been performed describing the electronic structures and transport properties of one-dimensional arrays of closely related phthalocyanines. 52−54 It is also necessary to mention two more recent theoretical studies of 1D-arrays/stacks formation by core-modified porphyrins: 21,23-dioxaporphyrin 55 and completely P-substituted 56−60 porphyrin ZnP(P) 4 . 61 In 2016, Jentzen, Shelnutt, and Scheidt reported the novel procedures for the purification and subsequent crystallization of the four metalloporphines, the simplest possible porphyrin derivatives containing Co(II), Cu(II), Pt(II), and Zn(II).…”

Quantum chemical studies of porphyrin‐ and expanded porphyrin‐based systems and their potential applications in nanoscience. Latin America research review

“…Other studies include the CT in nanoaggregates of complexes formed by 21,23‐dioxaporphyrin and neutral atoms of Zn, Cd, Cu, Ag, and Au (Figure ) . The nanoarrays were held together mostly by dispersion forces and presented band gaps smaller than 1 eV.…”

“…Spin density surface of a complex formed by 10 anionic 21,23‐dioxaporphyrin‐Cu units. (Reproduced with permission from Springer …”

Facile synthesis of 5-hydroxymethylfurfural: a sustainable raw material for the synthesis of key intermediates toward 21,23-dioxaporphyrins

“…Among the value added products, dioxaporphyrins are interesting molecular skeletons capable of forming stable complexes with neutral atoms and nanoaggregates with good charge mobility. 21 The current synthesis of 21,23-dioxaporphyrins involves complex synthetic procedures, low yield, and difficulties in isolation. 22 For the rst time, we have designed a very simple synthetic methodology to access 21,23-dioxaporphyrins through furanylpyrrolyl carbinols utilizing biomass derived HMF as a starting material (Scheme 1).…”