Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Properties and Molecular Nonlinearity

Optical Nonlinearity ◽

Nonlinear Properties ◽

Photoelectric Performance ◽

Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlinear properties observed in the experiment can be perfectly replicated, our theoretical calculations explored the essential characteristics of the optical properties of the mesoionic compounds with different electron-donating groups at the level of electronic structures through various wave function analysis methods. The influence of the electron-donating ability of the donor on the optical properties of the molecules and the contribution of the mesoionic ring moiety to their optical nonlinearity are clarified, which have not been reported by any research so far. This work will help people understand the nature of optical properties of mesoionic-based molecules and provide guidance for the rational design of molecules with excellent photoelectric performance in the future.

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

10.26434/chemrxiv.13525505 ◽

2021 ◽

Author(s):

Shugui Hua ◽

Zeyu Liu ◽

Tian Lu

Keyword(s):

Optical Properties ◽

External Field ◽

Rational Design ◽

Function Analysis ◽

Optical Nonlinearity ◽

Photophysical Property ◽

Polarizability Tensor ◽

Mesoionic Compound ◽

Density Analysis ◽

The photophysical property and optical nonlinearity of an electronic push-pull mesoionic compond, 2-(4-trifluoromethophenyl)-3-methyl-4-(4-methoxyphenyl)-1,3-thiazole-5-thiolate were theoretically investigated with a reliable computing strategy. The essence of the optical properties were then explored through a variety of wave function analysis methods, such as the natural transition orbital analysis, hole-electron analysis, (hyper)polarizability density analysis, decomposition of the (hyper)polarizability contribution by numerical integration, and (hyper)polarizability tensor analysis, at the level of electronic structures. The influence of the electric field and solvation on the electron absorption spectra and (hyper)polarizabilities of the molecule are highlighted and clarified. This work will help people to understand the influence of external field wavelength and solvent on the optical properties of mesoionic-based molecules, and provide a theoretical reference for the rational design of chromophores with adjustable properties in the future.

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

10.26434/chemrxiv.13525505.v1 ◽

2021 ◽

Author(s):

Shugui Hua ◽

Zeyu Liu ◽

Tian Lu

Keyword(s):

Optical Properties ◽

External Field ◽

Rational Design ◽

Function Analysis ◽

Optical Nonlinearity ◽

Photophysical Property ◽

Polarizability Tensor ◽

Mesoionic Compound ◽

Density Analysis ◽

The photophysical property and optical nonlinearity of an electronic push-pull mesoionic compond, 2-(4-trifluoromethophenyl)-3-methyl-4-(4-methoxyphenyl)-1,3-thiazole-5-thiolate were theoretically investigated with a reliable computing strategy. The essence of the optical properties were then explored through a variety of wave function analysis methods, such as the natural transition orbital analysis, hole-electron analysis, (hyper)polarizability density analysis, decomposition of the (hyper)polarizability contribution by numerical integration, and (hyper)polarizability tensor analysis, at the level of electronic structures. The influence of the electric field and solvation on the electron absorption spectra and (hyper)polarizabilities of the molecule are highlighted and clarified. This work will help people to understand the influence of external field wavelength and solvent on the optical properties of mesoionic-based molecules, and provide a theoretical reference for the rational design of chromophores with adjustable properties in the future.

Tuning Electronic Structure and Optical Properties of Li@cyclo[18]carbon Complex via Switching Doping Position of Lithium Atom

10.26434/chemrxiv.14601168.v1 ◽

2021 ◽

Author(s):

Zeyu Liu ◽

Xia Wang ◽

Tian Lu ◽

Aihua Yuan ◽

Xiufen Yan

Keyword(s):

Optical Properties ◽

Electronic Structure ◽

Function Analysis ◽

Molecular Switches ◽

Theoretical Work ◽

Optical Nonlinearity ◽

Metal Atoms ◽

Calculation Results ◽

Nanocarbon Materials ◽

Doping alkali metal atoms, especially lithium (Li), in nanocarbon materials has always been considered as one of the most effective methods to improve the optical properties of the system. In this theoretical work, we doped a Li atom into the recently observed all-carboatomic molecule, cyclo[18]carbon (C18), and finally obtained two stable configurations with Li inside and outside the ring. The calculation results show that the energy barrier of transition between the two Li@C18 complexes is quite low, and thus the conversion is easy to occur at ambient temperature. Importantly, the electronic structure, absorption spectrum, and optical nonlinearity of the two configurations are found to be significantly different, which indicates that the electronic structure and optical properties of the Li@C18 complex can be effectively regulated by switching the location of the doped Li atom between inside and outside the carbon ring. With the help of a variety of wave function analysis techniques, the nature of the discrepancies in the properties of the Li@C18 complex with different configurations has been revealed in depth. The relevant results of this work are expected to provide theoretical guidance for the future development of cyclocarbon-based optical molecular switches.

Tuning Electronic Structure and Optical Properties of Li@cyclo[18]carbon Complex via Switching Doping Position of Lithium Atom

10.26434/chemrxiv.14601168 ◽

2021 ◽

Author(s):

Zeyu Liu ◽

Xia Wang ◽

Tian Lu ◽

Aihua Yuan ◽

Xiufen Yan

Keyword(s):

Optical Properties ◽

Electronic Structure ◽

Function Analysis ◽

Molecular Switches ◽

Theoretical Work ◽

Optical Nonlinearity ◽

Metal Atoms ◽

Calculation Results ◽

Nanocarbon Materials ◽

Doping alkali metal atoms, especially lithium (Li), in nanocarbon materials has always been considered as one of the most effective methods to improve the optical properties of the system. In this theoretical work, we doped a Li atom into the recently observed all-carboatomic molecule, cyclo[18]carbon (C18), and finally obtained two stable configurations with Li inside and outside the ring. The calculation results show that the energy barrier of transition between the two Li@C18 complexes is quite low, and thus the conversion is easy to occur at ambient temperature. Importantly, the electronic structure, absorption spectrum, and optical nonlinearity of the two configurations are found to be significantly different, which indicates that the electronic structure and optical properties of the Li@C18 complex can be effectively regulated by switching the location of the doped Li atom between inside and outside the carbon ring. With the help of a variety of wave function analysis techniques, the nature of the discrepancies in the properties of the Li@C18 complex with different configurations has been revealed in depth. The relevant results of this work are expected to provide theoretical guidance for the future development of cyclocarbon-based optical molecular switches.

A Unique Class of Near-Infrared Functional Fluorescent Dyes with Carboxylic-Acid-Modulated Fluorescence ON/OFF Switching: Rational Design, Synthesis, Optical Properties, Theoretical Calculations, and Applications for Fluorescence Imaging in Living Animals

Journal of the American Chemical Society ◽

10.1021/ja209292b ◽

2012 ◽

Vol 134 (2) ◽

pp. 1200-1211 ◽

Cited By ~ 324

Author(s):

Lin Yuan ◽

Weiying Lin ◽

Yueting Yang ◽

Hua Chen

Keyword(s):

Optical Properties ◽

Carboxylic Acid ◽

Fluorescence Imaging ◽

Rational Design ◽

Near Infrared ◽

Fluorescent Dyes ◽

Theoretical Calculations ◽

Design Synthesis ◽

Modulated Fluorescence

Rational design of cyclopenta[b]naphthalenes for better optoelectronic applications and their photophysical properties using DFT/TD-DFT methods

RSC Advances ◽

10.1039/c6ra04844g ◽

2016 ◽

Vol 6 (50) ◽

pp. 44569-44577 ◽

Cited By ~ 8

Author(s):

Rajangam Jagadeesan ◽

Gunasekaran Velmurugan ◽

Ponnambalam Venuvanalingam

Keyword(s):

Optical Properties ◽

Dft Calculations ◽

Rational Design ◽

Dft Methods ◽

Td Dft ◽

Optoelectronic Applications

The optical properties of cyclopenta[b]naphthalenes (CPNs) can be fine-tuned by suitable substitutions and DFT calculations show that they can make efficient OLEDs.

Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

Frontiers in Chemistry ◽

10.3389/fchem.2021.786036 ◽

2021 ◽

Vol 9 ◽

Author(s):

Eline Desmedt ◽

Tatiana Woller ◽

Jos L. Teunissen ◽

Freija De Vleeschouwer ◽

Mercedes Alonso

Keyword(s):

Rational Design ◽

Nonlinear Optical ◽

Rayleigh Scattering ◽

Molecular Design ◽

Search Algorithm ◽

Molecular Switches ◽

Fine Tuning ◽

Structure Property ◽

Geometrical Properties

In the search for new nonlinear optical (NLO) switching devices, expanded porphyrins have emerged as ideal candidates thanks to their tunable chemical and photophysical properties. Introducing meso-substituents to these macrocycles is a successful strategy to enhance the NLO contrasts. Despite its potential, the influence of meso-substitution on their structural and geometrical properties has been scarcely investigated. In this work, we pursue to grasp the underlying pivotal concepts for the fine-tuning of the NLO contrasts of hexaphyrin-based molecular switches, with a particular focus on the first hyperpolarizability related to the hyper-Rayleigh scattering (βHRS). Building further on these concepts, we also aim to develop a rational design protocol. Starting from the (un)substituted hexaphyrins with various π-conjugation topologies and redox states, structure-property relationships are established linking aromaticity, photophysical properties and βHRS responses. Ultimately, inverse molecular design using the best-first search algorithm is applied on the most favorable switches with the aim to further explore the combinatorial chemical compound space of meso-substituted hexaphyrins in search of high-contrast NLO switches. Two definitions of the figure-of-merit of the switch performance were used as target objectives in the optimization problem. Several meso-substitution patterns and their underlying characteristics are identified, uncovering molecular symmetry and the electronic nature of the substituents as the key players for fine-tuning the βHRS values and NLO contrasts of hexaphyrin-based switches.

Rational design of polymers for optoelectronic interests

Pure and Applied Chemistry ◽

10.1351/pac200173020243 ◽

2001 ◽

Vol 73 (2) ◽

pp. 243-246 ◽

Cited By ~ 9

Author(s):

Tien-Yau Luh ◽

Ruey-Min Chen ◽

Tsyr-Yuan Hwu ◽

Sourav Basu ◽

Chung-Wai Shiau ◽

...

Keyword(s):

Optical Properties ◽

Rational Design ◽

Nonlinear Optical ◽

Nonlinear Optical Properties ◽

Organometallic Catalysts ◽

New Class

Using organometallic catalysts, two types of polymers containing conjugated moiety and insulating linker are synthesized. The investigations on the photophysical properties of these polymers (photoluminescence, electroluminescence and nonlinear optical properties) are briefly summarized. These polymers represent a new class of materials for optoelectronic interests.

Stoichiometric modulation on optical nonlinearity of 2D MoS x Se2−x alloys for photonic applications

Nanophotonics ◽

10.1515/nanoph-2021-0474 ◽

2021 ◽

Vol 0 (0) ◽

Author(s):

Xiaoli Sun ◽

Yuanyuan Wang ◽

Bingzheng Yan ◽

Kejian Yang ◽

Wei Wei ◽

...

Keyword(s):

Optical Properties ◽

Solid State ◽

Nonlinear Optical ◽

Theoretical Calculations ◽

Transition Metal Dichalcogenides ◽

Optical Nonlinearity ◽

Saturable Absorption ◽

Light Modulation ◽

Carrier Effective Mass ◽

Metal Dichalcogenides

Abstract The composition-engineered band structures of two-dimensional (2D) ternary transition-metal dichalcogenides (TMDCs) semiconductor alloys directly dominate their electronic and optical properties. Herein, in this paper, a detailed theoretical and experimental study on the composition-dependent nonlinear optical properties of 2D MoS x Se2−x alloys was carried out. The first-principles calculations were performed to investigate the compositionally modulated properties of monolayer 2D MoS x Se2−x (x = 0.25, 0.5, 1.0, 1.5, and 1.75) in terms of the carrier effective mass, carrier density and mobility, as well as band-gaps. Furthermore, high-quality few-layered MoS x Se2−x (x = 0.2, 0.5, 1.0, 1.5, and 1.8) nanosheets were fabricated by using liquid phase exfoliation method. The third-order nonlinear optical response was investigated by open-aperture Z-scan technique, revealing composition-dependent saturable absorption, and light modulation properties, which were correlated to the theoretical calculations and further confirmed by using MoS x Se2−x nanosheets as saturable absorbers (SAs) for all-solid-state pulsed lasers. In particular, a mode-locked solid-state laser with pulse width of 227 fs was realized with MoS0.2Se1.8 as SA, for the first time to our best knowledge. Our work not only provides a comprehensive understanding of the compositionally and defectively modulated nonlinear optical responses of ternary TMDCs alloys, but also paves a way for the development of 2D materials-based novel optoelectronic devices.