Abstract
With their versatile molecular topology and aromaticity, porphyrinoid systems combine remarkable chemistry with interesting photophysical properties and nonlinear optical properties. Hence, the field of application of porphyrinoids is very broad ranging from near-infrared dyes to opto-electronic materials. From previous experimental studies, aromaticity emerges as an important concept in determining the photophysical properties and two-photon absorption cross sections of porphyrinoids. Despite a considerable number of studies on porphyrinoids, few investigate the relationship between aromaticity, UV/vis absorption spectra and nonlinear properties. To assess such structure-property relationships, we performed a computational study focusing on a series of Hückel porphyrinoids to: (i) assess their (anti)aromatic character; (ii) determine the fingerprints of aromaticity on the UV/vis spectra; (iii) evaluate the role of aromaticity on the NLO properties. Using an extensive set of aromaticity descriptors based on energetic, magnetic, structural, reactivity and electronic criteria, the aromaticity of [4n+2] π-electron porphyrinoids was evidenced as was the antiaromaticity for [4n] π-electron systems. In agreement with previous studies, the absorption spectra of aromatic systems display more intense B and Q bands in comparison to their antiaromatic homologues. The nature of these absorption bands was analyzed in detail in terms of polarization, intensity, splitting and composition. Finally, quantities such as the average polarizability and its anisotropy were found to be larger in aromatic systems, whereas first and second hyperpolarizability are influenced by the interplay between aromaticity, planarity and molecular symmetry. To conclude, aromaticity dictates the photophysical properties in porphyrinoids, whereas it is not the only factor determining the magnitude of NLO properties.
Highlights
Porphyrinoids are macrocyclic compounds consisting of five-membered rings connected either directly or by bridging atoms, which usually exhibit a high degree of π-conjugation [1]
We focus on two measurable second-order nonlinear optical (NLO) responses: the hyper-Rayleigh scattering (HRS) response and the electric-field-induced second harmonic generation electric-field induced SHG (EFISHG) response (β//) [64,65]
We have investigated the aromaticity, photophysical properties and nonlinear optical properties of a series of porphyrinoids (16N, 16P, 18P, 18Py, 20P, 20O, 22S, 22I and 22Sp) differing in conjugation pathway length and aromaticity but sharing a Hückel topology
Summary
Porphyrinoids are macrocyclic compounds consisting of five-membered rings connected either directly or by bridging atoms, which usually exhibit a high degree of π-conjugation [1]. The extended π-conjugation system of expanded porphyrins enhances their conformational flexibility and they are ideal platforms to realize Möbius aromatic and antiaromatic species as well as figure-eight structures [4]. This huge structural diversity has led to a range of applications, including ion sensors [5], near-infrared (NIR) dyes [6], materials with two-photon absorption [7] and other nonlinear optical (NLO) properties [8] and molecular switches [9]. Optical and photophysical properties of porphyrinoids, these systems constitute a promising building block for molecular optoelectronic devices [10]
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