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Reversible π-system switching of thiophene-fused thiahexaphyrins by solvent and oxidation/reduction.

ABSTRACT: The concept of chemical topology has generated considerable interest among chemists and one of the state-of-the-art topics is Möbius topology in cyclic π-conjugated molecules. In this regard, expanded porphyrins have been extensively studied because of their facile topological interconversions and attractive optoelectronic properties. A typical example involves [28]hexaphyrins: they show topological conversion between planar Hückel and twisted Möbius topologies owing to their flexible structure. With this in mind, we designed a [28]hexaphyrin where one dimethine pyrrole unit was replaced with dithieno[3,4-b:3',4'-d]thiophene (β-DTT), aiming at a reversible switching between macrocyclic and cross-conjugated π-systems by a change in molecular topologies. Considering that the β-DTT unit can offer both macrocyclic and cross-conjugated π-circuits, we envisioned that a combination of the topological interconversion of [28]hexaphyrin with the two π-circuits of the β-DTT unit would enable a reversible switching between macrocyclic and cross-conjugated π-circuits on Möbius and Hückel topologies, respectively, by a simple conformational change. Unexpectedly, the hexaphyrin revealed a unique, unprecedented π-system switching between a Möbius cross-conjugated π-system and a Hückel antiaromatic π-system, which was fully supported by both experimental and theoretical investigations. Meanwhile, the [28]hexaphyrin was also found to be redox interconvertible with the corresponding [26]hexaphyrin with a Hückel cross-conjugated π-system. These results demonstrate that the β-DTT unit is a new effective motif to realize π-system switching by changing molecular and π-system topologies. Importantly, external stimuli, i.e., solvent, as well as oxidation/reduction can be used to trigger the topological changes in expanded porphyrins with the help of the β-DTT unit.

SUBMITTER: Higashino T

PROVIDER: S-EPMC6179095 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The reaction mechanisms and kinetics of thiophene oxidation reactions initiated by hydroperoxyl radical, and decomposition of the related intermediates and complexes, have been considered herein by using high-level DFT and ab initio calculations. The main energetic parameters of all stationary points of the suggested potential energy surfaces have been computed at the BD(T) and CCSD(T) methods, based on the geometries optimized at the B3LYP/6-311 + g(d,p) level of theory. Rate constants of bimolecular reactions (high-pressure limit rate constants) at temperatures from 300 to 3000 K for the first steps of the title reaction have been obtained through the conventional transition state theory (TST), while the pressure dependent rate constants and the rate constants of the second and other steps have been calculated employing the Rice-Ramsperger-Kassel-Marcus/Master equation (RRKM/ME). The results show that the rate constants of addition to α and β carbons have positive temperature dependence and negative pressure dependence. It is found that the additions of HO2 to the α and β carbons of thiophene in the initial steps of the title reaction are the most favored pathways. Also, the addition to the sulfur atom has a minor contribution. But, all efforts for simulating hydrogen abstraction reactions have been unsuccessful. In this complex oxidation reaction, about 12 different products are obtained, including important isomers such as thiophene-epoxide, thiophene-ol, thiophene-oxide, oxathiane, and thiophenone. The calculated total rate constants for generation of all minimum stationary points show that the addition reactions to the α and β carbons are the fastest among all at temperatures below 1000 K, while the proposed multi-step parallel reactions are more competitive at temperatures above 1200 K. Furthermore, important inter-and intra-molecular interactions for some species have been investigated by two well-known quantum chemistry method, the NBO and AIM analyses. Thermochemical properties such as free energy, enthalpy, internal energy, and entropy for thiophene and hydroperoxyl radical and related species in the simulated reactions have been predicted using a combination of the B3LYP and BD(T) methods.

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Reversible π-system switching of thiophene-fused thiahexaphyrins by solvent and oxidation/reduction.

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