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Effect of Exocyclic Substituents and ?-System Length on the Electronic Structure of Chichibabin Diradical(oid)s.

ABSTRACT: The ground state (GS) of Chichibabin's polycyclic hydrocarbons (CPHs) can be singlet [open- or closed-shell (OSS or CS)] or triplet (T), depending on the elongation of the ?-system and the exocyclic substituents. CPHs with either a small singlet-triplet energy gap (?E _ST) or even a triplet GS have potential applications in optoelectronics. To analyze the effect of the size and exocyclic substituents on the nature of the GS of CPHs, we have selected a number of them with different substituents in the exocyclic carbon atoms and different ring chain lengths. The OPBE/cc-pVTZ level of theory was used for the optimization of the systems. The aromaticity of the resulting electronic structures was evaluated with HOMA, NICS, FLU, PDI, I_ring, and MCI aromaticity indices. Our results show that the shortest ?-systems (one or two rings) have a singlet GS. However, systems with three to five rings favor OSS GSs. Electron-withdrawing groups (EWGs) and aromatic substituents in the exocyclic carbons tend to stabilize the OSS and T states, whereas electron-donating groups slightly destabilize them. For CS, OSS, and T states, aromaticity measures indicate a gain of aromaticity of the 6-membered rings of the CPHs with the increase in their size and when CPHs incorporate EWGs or aromatic substituents. In general, the CPHs analyzed present small singlet-triplet energy gaps, and in particular, the ones containing EWGs or aromatic substituents present the smallest singlet-triplet energy gaps.

SUBMITTER: Escayola S

PROVIDER: S-EPMC6648453 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Effect of Exocyclic Substituents and π-System Length on the Electronic Structure of Chichibabin Diradical(oid)s.

Escayola Sílvia S Callís Marc M Poater Albert A Solà Miquel M

ACS omega 20190621 6

The ground state (GS) of Chichibabin's polycyclic hydrocarbons (CPHs) can be singlet [open- or closed-shell (OSS or CS)] or triplet (T), depending on the elongation of the π-system and the exocyclic substituents. CPHs with either a small singlet-triplet energy gap (Δ<i>E</i> <sub>ST</sub>) or even a triplet GS have potential applications in optoelectronics. To analyze the effect of the size and exocyclic substituents on the nature of the GS of CPHs, we have selected a number of them with differe ...[more]

PMID: 31460182

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Project description:Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. DFT remains the workhorse for modeling such extended macrocycles, when taking into account their size and huge conformational flexibility. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, π···π stacking, steric effects, ring strain, and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wave function methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a stronger degree of static correlation than the Hückel and twisted-Hückel structures, and as a result the relative energies of singly twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between the extrapolated MP2/CBS energies estimated from cc-pV{T,Q}Z, diffuse-augmented heavy-aug-cc-pV{T,Q}Z and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol-1 with the CCSD(T) relative energies. Regarding DFT methods, the range-separated double hybrids, such as ωB97M(2) and B2GP-PLYP, outperform other functionals with RMSDs of 0.6 and 0.8 kcal mol-1, respectively. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended π-systems, the errors drop down to 1.9 kcal mol-1 for the revised revDOD-PBEP86-NL, which eliminates the same-spin correlation energy. Minnesota meta-GGA functionals with high fractions of exact exchange (M06-2X and M08-HX) also perform reasonably well, outperforming more robust and significantly less empirically parametrized functionals like SCAN0-D3.

Dataset Information

Effect of Exocyclic Substituents and ?-System Length on the Electronic Structure of Chichibabin Diradical(oid)s.

Publications

Effect of Exocyclic Substituents and π-System Length on the Electronic Structure of Chichibabin Diradical(oid)s.

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