Dataset Information

Hemithioindigo-Based Trioxobicyclononadiene: 3D Multiswitching of Electronic and Geometric Properties.

ABSTRACT: Molecular photoswitches that offer simultaneous precise control over geometrical and electronic changes are rare yet highly sought tools for the development of responsive nanosystems. Here we present such an advantageous combination of property control within a novel multiphotoswitch architecture. Hemithioindigo-based trioxobicyclononadiene (HTI-TOND) offers a rigid three-dimensional molecular structure that undergoes different exotic rearrangement reactions upon photochemical and thermal signaling. Three to four different states with distinct geometric and electronic properties can be accessed reversibly in high yields within this molecular framework. Thus, a highly promising and unique switching tool has become available to instill the next level of addressability at the smallest scales.

SUBMITTER: Kohl F

PROVIDER: S-EPMC8874893 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Publications

Hemithioindigo-Based Trioxobicyclononadiene: 3D Multiswitching of Electronic and Geometric Properties.

Kohl Fabien F Gerwien Aaron A Hampel Frank F Mayer Peter P Dube Henry H

Journal of the American Chemical Society 20220214 7

Molecular photoswitches that offer simultaneous precise control over geometrical and electronic changes are rare yet highly sought tools for the development of responsive nanosystems. Here we present such an advantageous combination of property control within a novel multiphotoswitch architecture. Hemithioindigo-based trioxobicyclononadiene (HTI-TOND) offers a rigid three-dimensional molecular structure that undergoes different exotic rearrangement reactions upon photochemical and thermal signal ...[more]

PMID: 35157795

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Project description:Here, the ground-state structures, electronic structures, polarizability, and spectral properties of metal-free phthalocyanine (H2Pc) under different external electric fields (EEFs) are investigated. The results show that EEF has an ultrastrong regulation effect on various aspects of H2Pc; the geometric structures, electronic properties, polarizability, and spectral properties are strongly sensitive to the EEF. In particular, an EEF of 0.025 a.u. is an important control point: an EEF of 0.025 a.u. will bend the benzene ring subunits to the positive and negative x directions of the planar molecule. Flipping the EEF from positive (0.025 a.u.) to negative (-0.025 a.u.) flips also the bending direction of benzene ring subunits. The H2Pc shows different dipole moments projecting an opposite direction along the x direction (-84 and 84 Debye for EEFs of -0.025 and 0.025 a.u., respectively) under negative and positive EEF, revealing a significant dipole moment transformation. Furthermore, when the EEF is removed, the molecule can be restored to the planar structure. The transformation of the H2Pc structure can be induced by the EEF, which has potential applications in the molecular devices such as molecular switches or molecular forceps. EEF lowers total energy and reduces highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap; especially, an EEF of 0.025 a.u. can reduce the HOMO-LUMO gap from 2.1 eV (in the absence of EEF) to 0.37 eV, and thus, it can enhance the molecular conductivity. The first hyperpolarizability of H2Pc is 0 in the absence of EEF; remarkably, an EEF of 0.025 a.u. can enhance the first hyperpolarizability up to 15,578 a.u. Therefore, H2Pc under the EEF could be introduced as a promising innovative nonlinear optical (NLO) nanomaterial such as NLO switches. The strong EEF (0.025 a.u.) causes a large number of new absorption peaks in IR and Raman spectra and causes the redshift of electronic absorption spectra. The changes of EEF can be used to regulate the structure transformation and properties of H2Pc, which can promote the application of H2Pc in nanometer fields such as molecular devices.

Dataset Information

Hemithioindigo-Based Trioxobicyclononadiene: 3D Multiswitching of Electronic and Geometric Properties.

Publications

Hemithioindigo-Based Trioxobicyclononadiene: 3D Multiswitching of Electronic and Geometric Properties.

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