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

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 ◽  
Photophysical Properties ◽  
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.

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

2020 ◽  
Author(s):  
Zeyu Liu ◽  
Shugui Hua ◽  
Tian Lu ◽  
Ziqi Tian
Keyword(s):  
Optical Properties ◽  
Rational Design ◽  
Rayleigh Scattering ◽  
Function Analysis ◽  
Theoretical Calculations ◽  
Photophysical Properties ◽  
Optical Nonlinearity ◽  
Nonlinear Properties ◽  
Photoelectric Performance ◽  
Wave Function Analysis

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.

Structural modification strategies for the rational design of red/NIR region BODIPYs

2014 ◽  
Vol 43 (13) ◽  
pp. 4778-4823 ◽  
Author(s):  
Hua Lu ◽  
John Mack ◽  
Yongchao Yang ◽  
Zhen Shen
Keyword(s):  
Rational Design ◽  
Structural Modification ◽  
Photophysical Properties ◽  
Structure Property ◽  
Structure Property Relationships

The structure–property relationships of red/NIR region BODIPY dyes is analyzed, so that trends in their photophysical properties can be readily compared.

scholarly journals Combining Defects in a Single Nanographene: A Fully Helical Saddle Ribbon

Synlett ◽  
2019 ◽  
Vol 30 (09) ◽  
pp. 997-1002 ◽  
Author(s):  
Carlos Cruz ◽  
Silvia Castro-Fernández ◽  
Ermelinda Maçôas ◽  
Alba Millán ◽  
Araceli Campaña
Keyword(s):  
Organic Synthesis ◽  
Carbon Nanostructures ◽  
Nonlinear Optical ◽  
Photophysical Properties ◽  
Structure Property ◽  
Chiroptical Properties ◽  
Curved Structures ◽  
Structure Property Relationships ◽  
Linear And Nonlinear ◽  
Controlled Preparation

The controlled preparation of well-defined distorted nanographenes by a bottom-up approach based on organic synthesis permits the direct establishment of unprecedented structure–property relationships in carbon nanostructures. The simultaneous incorporation of various defects in nanographenes affords highly curved structures with novel or enhanced photophysical properties. In this sense, we recently reported a fully helical and saddle-shaped nanographene ribbon containing the first undecabenzo[7]helicene unit. Both its linear and nonlinear optical properties are enhanced in comparison with those of other partially π-extended [7]helicenes. Moreover, the new superhelicene exhibits the highest emission dissymmetry factor (g lum) reported to date for a homochiral nanographene. The combination of both nonlinear and chiroptical properties in nanographenes opens up new possible future applications for those distorted nanostructures.1 Introduction2 Synthesis of Embedded Seven-Membered Rings3 Combination of Defects: Seven-Membered Rings and π-Extended Helicenes4 Conclusions and Outlook

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

2020 ◽  
Author(s):  
Zeyu Liu ◽  
Shugui Hua ◽  
Tian Lu ◽  
Ziqi Tian
Keyword(s):  
Optical Properties ◽  
Rational Design ◽  
Rayleigh Scattering ◽  
Function Analysis ◽  
Theoretical Calculations ◽  
Photophysical Properties ◽  
Optical Nonlinearity ◽  
Nonlinear Properties ◽  
Photoelectric Performance ◽  
Wave Function Analysis

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.

scholarly journals Rational design of polymers for optoelectronic interests

2001 ◽  
Vol 73 (2) ◽  
pp. 243-246 ◽  
Author(s):  
Tien-Yau Luh ◽  
Ruey-Min Chen ◽  
Tsyr-Yuan Hwu ◽  
Sourav Basu ◽  
Chung-Wai Shiau ◽  
...  
Keyword(s):  
Optical Properties ◽  
Rational Design ◽  
Nonlinear Optical ◽  
Photophysical Properties ◽  
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.

scholarly journals Methodologies in Spectral Tuning of DSSC Chromophores through Rational Design and Chemical-Structure Engineering

Materials ◽  
2019 ◽  
Vol 12 (24) ◽  
pp. 4024 ◽  
Author(s):  
Qudsia Arooj ◽  
Gregory J. Wilson ◽  
Feng Wang
Keyword(s):  
Solar Cell ◽  
Rational Design ◽  
Molecular Design ◽  
Dye Sensitized Solar Cells ◽  
Organic Dye ◽  
Structure Property ◽  
Design Strategies ◽  
Design And Synthesis ◽  
Dye Sensitized ◽  
Structure Property Relationships

The investigation of new photosensitizers for Grätzel-type organic dye-sensitized solar cells (DSSCs) remains a topic of interest for researchers of alternative solar cell materials. Over the past 20 years, considerable and increasing research efforts have been devoted to the design and synthesis of new materials, based on “donor, π-conjugated bridge, acceptor” (D–π–A) organic dye photosensitizers. In this paper, the computational chemistry methods are outlined and the design of organic sensitizers (compounds, dyes) is discussed. With reference to recent literature reports, rational molecular design is demonstrated as an effective process to study structure–property relationships. Examples from established organic dye sensitizer structures, such as TA-St-CA, Carbz-PAHTDDT (S9), and metalloporphyrin (PZn-EDOT), are used as reference structures for an examination of this concept applied to generate systematically modified structural derivatives and hence new photosensitizers (i.e., dyes). Using computer-aided rational design (CARD), the in silico design of new chromophores targeted an improvement in spectral properties via the tuning of electronic structures by substitution of molecular fragments, as evaluated by the calculation of absorption profiles. This mini review provides important rational design strategies for engineering new organic light-absorbing compounds towards improved spectral absorption and related optoelectronic properties of chromophores for photovoltaic applications, including the dye-sensitized solar cell (DSSC).

Rigid Optical Chromophore: The Photophysical Properties of p-Phenylene Benzobisthiazole Derivative

2001 ◽  
Vol 708 ◽  
Author(s):  
Seung-Hwan Lee ◽  
Akira Otomo ◽  
Tatsuo Nakahama ◽  
Toshiki Yamada ◽  
Shiyoshi Yokoyama ◽  
...  
Keyword(s):  
Nonlinear Optical ◽  
Rayleigh Scattering ◽  
Photophysical Properties ◽  
Nitrogen Atmosphere ◽  
Good Thermal Stability ◽  
Donor And Acceptor ◽  
Scattering Technique ◽  
Optical Applications ◽  
Nonlinear Optical Applications ◽  
Propanol Solution

ABSTRACTA novel rigid and planar chromophore, p-phenylene benzobisthiazole unit with donor and acceptor groups, has been synthesized for second-order nonlinear optical applications. The first hyperpolarizability, β, of the nonlinear optical (NLO) chromophore has been measured by a Hyper-Rayleigh Scattering technique at 1064 nm in 1,1,1,3,3,3-hexafluoro-2-propanol solution. The β value of the NLO chromophore is 405E-30 esu, which is about seventeen times that of the p-NA (nitroaniline) value. The chromophore showed good thermal stability up to 330 °C in nitrogen atmosphere.

Structure Property Characterization of Nonlinear Optical Materials

2004 ◽  
Vol 846 ◽  
Author(s):  
Joy E. Rogers ◽  
Jonathan E. Slagle ◽  
Daniel G. McLean ◽  
Benjamin C. Hall ◽  
Thomas M. Cooper ◽  
...  
Keyword(s):  
Nonlinear Optical ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Photophysical Properties ◽  
Excited State Absorption ◽  
Laser Flash ◽  
Nanosecond Laser ◽  
Structure Property ◽  
Absorption Properties ◽  
Structure Property Relationships

ABSTRACTThis research is comprised of understanding the linear photophysical properties of various dyes to better understand the more complicated nonlinear optical properties. Determining structure property relationships of a series of structurally closely related chromophores is the key in understanding the drivers for the various photophysical properties. In this paper we survey the effect of physically changing the Pt poly-yne structure on the S0-S1 and T1-Tn absorption properties for each of the chromophores. A series of structurally modified platinum poly-ynes have been studied using experimental methods including UV/Vis absorption and nanosecond laser flash photolysis. We found that with extension of the ligand length both the ground and triplet excited state absorption shift to lower energies. Comparing the absorption properties of the ligands and butadiynes with the platinum containing versions reveal that the S1 and Tn exciton is localized on one portion of the ligand with extension and not conjugated through the whole molecule. Changing the phosphine R group results in little effect to the absorption properties except when the R group is conjugated in the case of phenyl. However, changing the R group results in varied materials properties.

Exploration of Bis(Arylimidazole) Iridium Picolinate Complexes

2017 ◽  
Author(s):  
Aron Huckaba ◽  
sadig aghazada ◽  
iwan zimmermann ◽  
giulia grancini ◽  
natalia gasilova ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Photophysical Properties ◽  
Structure Property ◽  
Aryl Group ◽  
Ligand Modification ◽  
Property Relationship ◽  
Structure Property Relationship

The straightforward synthesis and photophysical properties of a new series of heteroleptic Iridium (III) bis(2-arylimidazole) picolinate complexes is reported. Each complex has been characterized by NMR, UV-Vis, cyclic voltammetry, and the emissive properties of each is described. By systematically modifying first the cyclometallating aryl group on the arylimidazole ligand and then the picolinate ligand, the ramifications of ligand modification in these complexes was better understood through the construction of a structure-property relationship.

Exploration of Bis(Arylimidazole) Iridium Picolinate Complexes

2017 ◽  
Author(s):  
Aron Huckaba ◽  
sadig aghazada ◽  
iwan zimmermann ◽  
giulia grancini ◽  
natalia gasilova ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Photophysical Properties ◽  
Structure Property ◽  
Aryl Group ◽  
Ligand Modification ◽  
Property Relationship ◽  
Structure Property Relationship

The straightforward synthesis and photophysical properties of a new series of heteroleptic Iridium (III) bis(2-arylimidazole) picolinate complexes is reported. Each complex has been characterized by NMR, UV-Vis, cyclic voltammetry, and the emissive properties of each is described. By systematically modifying first the cyclometallating aryl group on the arylimidazole ligand and then the picolinate ligand, the ramifications of ligand modification in these complexes was better understood through the construction of a structure-property relationship.

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