Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C18 to C16.

Recent advances in synthetic methods, combined with tip-induced on-surface chemistry, have enabled the formation of numerous cyclocarbon molecules. Here, we investigate computationally the experimentally studied C16 and C18 molecules as well as their van der Waals (vdW) complexes with several typical donor and acceptor molecules. Our results demonstrate a remarkable electron-withdrawing ability of cyclocarbon molecules. The vdW complexes of C16 and C18 exhibit a thermodynamically favorable photoinduced electron transfer (ET) from the donor partner to the cyclocarbons that occurs on a picosecond time scale. The lower reorganization energy of C16 compared to C18 leads to a significant acceleration of the ET reactions.

A step towards rational design of carbon nanobelts with tunable electronic properties.

Belt-shaped aromatic compounds are among the most attractive classes of radial π-conjugated nanocarbon molecules with unique physical and chemical properties. In this work, we computationally studied a number of all-carbon and heteroatom-bridged nanobelts, as well as their inclusion complexes with fullerene C60. Our results provide a useful guide for modulating the electronic properties of the nanobelts. An in-depth analysis of the ground and excited state properties of their complexes has allowed us to establish structure-property relationships and propose simple principles for the design of nanobelts with improved electron-donating properties suitable for photovoltaic applications.

Aromaticity controls the excited-state properties of host-guest complexes of nanohoops.

π-Conjugated organic molecules have exciting applications as materials for batteries, solar cells, light-emitting diodes, etc. Among these systems, antiaromatic compounds are of particular interest because of their smaller HOMO-LUMO energy gap compared to aromatic compounds. A small HOMO-LUMO gap is expected to facilitate charge transfer in the systems. Here we report the ground and excited-state properties of two model nanohoops that are nitrogen-doped analogs of recently synthesized [4]cyclodibenzopentalenes - tetramers of benzene-fused aromatic 1,4-dihydropyrrolo[3,2-b]pyrrole ([4]DHPP) and antiaromatic pyrrolo[3,2-b]pyrrole ([4]PP). Their complexes with C60 fullerene show different behavior upon photoexcitation, depending on the degree of aromaticity. [4]DHPP acts as an electron donor, whereas [4]PP is a stronger electron acceptor than C60. The ultrafast charge separation combined with the slow charge recombination that we found for [4]PP⊃C60 indicates a long lifetime of the charge transfer state.

Nitrogen-doped molecular bowls as electron donors in photoinduced electron transfer reactions.

In recent years, the chemistry of curved π-conjugated molecules has experienced a sharp rise. The inclusion of a heteroatom in the carbon network significantly affects its semiconducting properties. In this work, we computationally study the photoinduced electron transfer in a series of C60 fullerene complexes with experimentally established nitrogen-doped molecular bowls. Our results demonstrate that introducing nitrogen into pentagonal rings of the bowl-shaped π-conjugated molecules and extending the π-conjugation can modulate their electron-transfer properties. Among the studied complexes, the hub-NCor⊃C60 complex exhibits the most desirable combination of ultrafast charge separation and slow charge recombination, suggesting its potential use in photovoltaics.

Photoinduced electron transfer in non-covalent complexes of C60 and phosphangulene oxide derivatives.

Investigation of photoinduced electron transfer (PET) in a series of experimentally reported complexes of fullerene with phosphangulene oxides shows that the replacement of O atoms in the bridge of phosphangulene with S atoms promotes efficient and ultrafast ET from phosphangulene oxide to fullerene in PGOOSS⊃C60 and PGOSSS⊃C60 complexes. The results obtained can be useful for the development of photovoltaic devices based on phosphangulenes.

Photoinduced electron transfer in nano-Saturn complexes of fullerene.

The photoinduced electron transfer is studied computationally in several Saturn-shaped inclusion complexes of carbo-aromatic rings and C60 fullerene - C72⊃C60, C96⊃C60, C120⊃C60, and C168⊃C60. Analysis of their structural and electronic properties shows that the charge separation process is efficient in C120⊃C60 and C168⊃C60 where the host molecule resembles the conjugated [24]circulene unit. In contrast, the electron transfer is not feasible in the complexes of the oligophenylene-based rings C72⊃C60 and C96⊃C60.

Electron Transfer in a Li+-Doped Zn-Porphyrin-[10]CPP⊃Fullerene Junction and Charge-Separated Bands with Opposite Response to Polar Environments.

Recently synthesized porphyrin-cycloparaphenylene (ZnP-[10]CPP) junction is a powerful platform to develop useful organic photovoltaic devices. In this work, we computationally study photoinduced electron transfer processes in the supramolecular complex ZnP-[10]CPP⊃C60 and its Li+-doped derivative. The most striking finding is charge-separated (CS) bands in ZnP-[10]CPP⊃Li+@C60 with opposite response to solvent polarity. Besides CS bands that demonstrate a bathochromic shift, there exist CS transitions showing a rarely observed hypsochromic shift. The rates of energy transfer, charge separation, and charge recombination in the supramolecular complexes are computed by using the semiclassical approach. These estimates suggest that the both types of CS states can be efficiently populated in polar media by decay of locally excited states.

Photoinduced electron transfer and unusual environmental effects in fullerene-Zn-porphyrin-BODIPY triads.

Molecular arrays containing donor-acceptor sites and antenna molecules are promising candidates for organic photovoltaic devices. Photoinduced electron transfer (PET) in multi-chromophore systems is controlled by a subtle interplay of donor and acceptor properties and solvent effects. In the present study, we explore how PET of fullerene [C60]-Zn-porphyrin-BODIPY triads can be modulated by passing from non-polar to polar media. To this end we perform a computational study of this complex using the DFT/TDDFT method. We find that the stabilization energy of charge transfer states by a polar medium depends significantly on whether the BODIPY moiety acts as an electron donor or an electron acceptor. To understand this effect of the environment, a detailed analysis of the initial and final states of the ET reactions is performed. We show that additional deactivation channels of the porphyrin excited state may come into play as solvent polarity increases.

How amino and nitro substituents direct electrophilic aromatic substitution in benzene: an explanation with Kohn-Sham molecular orbital theory and Voronoi deformation density analysis.

The substituent effect of the amino and nitro groups on the electronic system of benzene has been investigated quantum chemically using quantitative Kohn-Sham molecular orbital theory and a corresponding energy decomposition analysis (EDA). The directionality of electrophilic substitution in aniline can accurately be explained with the amount of contribution of the 2pz orbitals on the unsubstituted carbon atoms to the highest occupied π orbital. For nitrobenzene, the molecular π orbitals cannot explain the regioselectivity of electrophilic substitution as there are two almost degenerate π orbitals with nearly the same 2pz contributions on the unsubstituted carbon atoms. The Voronoi deformation density analysis has been applied to aniline and nitrobenzene to obtain an insight into the charge rearrangements due to the substituent. This analysis method identified the orbitals involved in the C-N bond formation of the π system as the cause for the π charge accumulation at the ortho and para positions in the case of the NH2 group and the largest charge depletion at these same positions for the NO2 substituent. Furthermore, we showed that it is the repulsive interaction between the πHOMO of the phenyl radical and the πHOMO of the NH2 radical that is responsible for pushing up the πHOMO of aniline and therefore activating this π orbital of the phenyl ring towards electrophilic substitution.