Triply twisted Möbius annulene: a new class of two-photon active material – a computational study

Abstract

In the present work, we have studied the gas phase one- and two-photon absorption (OPA and TPA) properties of the first two excited states of the triply twisted Möbius annulene molecule (G. R. Schaller, et al., Nat. Chem. 2014, 6, 608) and five model systems substituted with different donor and acceptor groups. The main purpose of this study is to explore the OPA and TPA properties of this newly synthesized molecule and the unique π-conjugation provided by it. We have used the linear and quadratic response theory methods with the CAMB3LYP functional and the cc-pVDZ basis set for calculating the required parameters. Our results indicate that in the absence of any directive force (i.e. the donor-acceptor groups) the unsubstituted molecule is completely TP inactive. However, as soon as we insert the donor-acceptor group the system becomes TP active which can further be enhanced (up to 3640 GM in our case) by changing the donor-acceptor groups. We have explained the results by performing a two-state model calculation and by analyzing the TP tensor elements and the orbitals involved in the transition processes.

Cyclic tris-[5]helicenes with single and triple twisted Möbius topologies and Möbius aromaticity

“…Theoretical calculations predict that upon irradiation with a strong laser pulse (even in the absence of a magnetic field), ring currents should be induced which are orders of magnitude larger than the currents induced in a superconducting NMR magnet 35,36. Moreover, peculiar nonlinear optical37 and two photon absorption properties38 have been predicted for Möbius annulenes.…”

Design of Hückel–Möbius Topological Switches with High Nonlinear Optical Properties

“…For this purpose, it has been well-established in the literature that the computational theoryaided design can be a useful tool to optimize the molecular electro-optic performance. [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Recently, several works [45][46][47][48][49][50][51][52][53][54][55] have evaluated the NLOP of Hückel and Möbius topologies. For instance, the present authors studied the electronic and vibrational contributions to static and dynamic NLOP of the Hückel-Möbius switch of the bianthraquinodimethane modified [16] annulene 56,57 and A,D-di-p-benzi [28]hexaphyrin(1.1.1.1.1.1).…”

“…16 Our previous results indicated that these systems present high NLOP values and large differences between the Hückel and Möbius structures, pointing out their potential use as optical switches. Kundi et al 53 analyzed the gas phase one-and two-photon absorption properties of the first two excited states of the triply twisted Möbius annulene molecule 58 and five model systems substituted with different donor and acceptor groups using the response theory and two-state model approaches. It was found that the unsubstituted molecule is completely two-photon inactive and it becomes active with the introduction of strong donor-acceptor groups.…”

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

“…DFT calculations on the triply twisted annulene 176 and related macrocycles were recently reported from other research groups. [287][288][289][290] Miki, Ohe, and co-workers recently reported the 2,2'-diethynyl-1,1'-binaphthyl-containing carbon double helices ( Figure 56). [291] The precursor (S,S)-177 wass ynthesized by using macrocyclization under Sonogashira-Hagihara coupling conditions.…”

“…This molecule is the first example of a triply twisted Möbius annulene. DFT calculations on the triply twisted annulene 176 and related macrocycles were recently reported from other research groups …”