scholarly journals Porous Shape-Persistent Rylene Imine Cages with Tunable Optoelectronic Properties and Delayed Fluorescence

2020 ◽  
Author(s):  
Hsin-Hua Huang ◽  
Kyung Seob Song ◽  
Alessandro Prescimone ◽  
Rajesh Mannancherry ◽  
Ali Coskun ◽  
...  
Keyword(s):  
Excited State ◽  
Electronic Properties ◽  
Green Light ◽  
Delayed Fluorescence ◽  
Optoelectronic Properties ◽  
Covalent Organic Frameworks ◽  
Singlet Fission ◽  
Triplet Pair ◽  
Material Porosity

A simultaneous combination of porosity and tunable optoelectronic properties, common in covalent organic frameworks, are rare in shape-persistent organic cages. Yet, organic cages offer important molecular advantages, the solubility and modularity. Herein, we report the synthesis of a series of chiral imine organic cages with three built-in rylene units by means of dynamic imine chemistry and we investigate their textural and optoelectronic properties. Thereby we demonstrate that the synthesized rylene cages are porous, can be reversibly reduced at accessible potentials, and can absorb from UV up to green light. We also show that they preferentially adsorb CO2 over N2 and CH4 with a good selectivity. In addition, we discovered that the cage incorporating three perylene-3,4:9,10-bis(dicarboximide) units displays a delayed fluorescence, likely as a consequence of formation of a correlated triplet pair, the multiexciton state in singlet fission. Rylene cages thus represent a unique platform to investigate the effect of electronic properties on material porosity and, at the same time, to probe excited-state phenomena in the limit of vanishing interchromophore coupling. <br>

scholarly journals Porous Shape-Persistent Rylene Imine Cages with Tunable Optoelectronic Properties and Delayed Fluorescence

2020 ◽  
Author(s):  
Hsin-Hua Huang ◽  
Kyung Seob Song ◽  
Alessandro Prescimone ◽  
Rajesh Mannancherry ◽  
Ali Coskun ◽  
...  
Keyword(s):  
Excited State ◽  
Electronic Properties ◽  
Green Light ◽  
Delayed Fluorescence ◽  
Optoelectronic Properties ◽  
Covalent Organic Frameworks ◽  
Singlet Fission ◽  
Triplet Pair ◽  
Material Porosity

A simultaneous combination of porosity and tunable optoelectronic properties, common in covalent organic frameworks, are rare in shape-persistent organic cages. Yet, organic cages offer important molecular advantages, the solubility and modularity. Herein, we report the synthesis of a series of chiral imine organic cages with three built-in rylene units by means of dynamic imine chemistry and we investigate their textural and optoelectronic properties. Thereby we demonstrate that the synthesized rylene cages are porous, can be reversibly reduced at accessible potentials, and can absorb from UV up to green light. We also show that they preferentially adsorb CO2 over N2 and CH4 with a good selectivity. In addition, we discovered that the cage incorporating three perylene-3,4:9,10-bis(dicarboximide) units displays a delayed fluorescence, likely as a consequence of formation of a correlated triplet pair, the multiexciton state in singlet fission. Rylene cages thus represent a unique platform to investigate the effect of electronic properties on material porosity and, at the same time, to probe excited-state phenomena in the limit of vanishing interchromophore coupling. <br>

Triplet-Pair States in Organic Semiconductors

2019 ◽  
Vol 70 (1) ◽  
pp. 323-351 ◽  
Author(s):  
Andrew J. Musser ◽  
Jenny Clark
Keyword(s):  
Organic Semiconductors ◽  
First Principles ◽  
Delayed Fluorescence ◽  
Singlet Fission ◽  
Organic Semiconductor Materials ◽  
Materials Research ◽  
Triplet Pair ◽  
The 1960S ◽  
Pair State ◽  
Triplet Excitons

Entanglement of states is one of the most surprising and counterintuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic semiconductor materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which consists of a pair of localized triplet excitons coupled into an overall spin-0, -1, or -2 configuration. The most widely analyzed of these is the spin-0 pair, denoted1(TT), which was initially invoked in the 1960s to explain delayed fluorescence in acene films. It is considered an essential gateway state for triplet-triplet annihilation and the reverse process, singlet fission, enabling interconversion between one singlet and two triplet excitons without any change in overall spin. This state has returned to the forefront of organic materials research in recent years, thanks both to its central role in the resurgent field of singlet fission and to its implication in a host of exotic new photophysical behaviors. Here we review the properties of triplet-pair states, from first principles to recent experimental results.

Intercalation of First Row Transition Metals inside Covalent-Organic Frameworks (COF): a Strategy to Fine Tune the Electronic Properties of Porous Crystalline Materials

2018 ◽  
Author(s):  
Srimanta Pakhira ◽  
Jose Mendoza-Cortes
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Electronic Properties ◽  
High Surface ◽  
Electronic Devices ◽  
High Surface Area ◽  
Main Role ◽  
Covalent Organic Frameworks ◽  
Porous Network ◽  
Crystalline Materials

<div>Covalent organic frameworks (COFs) have emerged as an important class of nano-porous crystalline materials with many potential applications. They are intriguing platforms for the design of porous skeletons with special functionality at the molecular level. However, despite their extraordinary properties, it is difficult to control their electronic properties, thus hindering the potential implementation in electronic devices. A new form of nanoporous material, COFs intercalated with first row transition metal is proposed to address this fundamental drawback - the lack of electronic tunability. Using first-principles calculations, we have designed 31 new COF materials <i>in-silico</i> by intercalating all of the first row transition metals (TMs) with boroxine-linked and triazine-linked COFs: COF-TM-x (where TM=Sc-Zn and x=3-5). This is a significant addition considering that only 187 experimentally COFs structures has been reported and characterized so far. We have investigated their structure and electronic properties. Specifically, we predict that COF's band gap and density of states (DOSs) can be controlled by intercalating first row transition metal atoms (TM: Sc - Zn) and fine tuned by the concentration of TMs. We also found that the $d$-subshell electron density of the TMs plays the main role in determining the electronic properties of the COFs. Thus intercalated-COFs provide a new strategy to control the electronic properties of materials within a porous network. This work opens up new avenues for the design of TM-intercalated materials with promising future applications in nanoporous electronic devices, where a high surface area coupled with fine-tuned electronic properties are desired.</div>

The role of conformational heterogeneity in the excited state dynamics of linked diketopyrrolopyrrole dimers

2021 ◽  
Author(s):  
Siobhan Bradley ◽  
Ming Chi ◽  
Jonathan White ◽  
Christopher R. Hall ◽  
Lars Goerigk ◽  
...  
Keyword(s):  
Excited State ◽  
Conformational Heterogeneity ◽  
Singlet Fission ◽  
Excited State Dynamics

Diketopyrrolopyrrole (DPP) derivatives have been proposed for both singlet fission and energy upconversion as they meet the energetic requirements and exhibit superior photostability compared to many other chromophores. In this...

sp2 carbon-conjugated covalent organic frameworks: synthesis, properties, and applications

2021 ◽  
Vol 5 (7) ◽  
pp. 2931-2949
Author(s):  
Xinle Li
Keyword(s):  
Chemical Stability ◽  
Optoelectronic Properties ◽  
Covalent Organic Frameworks ◽  
High Crystallinity ◽  
Synthesis Properties

sp2 carbon-conjugated COFs (sp2c-COFs) featuring an unparalleled combination of sp2 carbon linkages, extended π-conjugation, high crystallinity, permanent porosity, unique optoelectronic properties, and extraordinary chemical stability, have garnered enormous attention recently.

Energetics and Optimal Molecular Packing for Singlet Fission in BN-doped Perylenes: Electronic Adiabatic State Basis Screening

2021 ◽  
Author(s):  
Anurag Singh ◽  
Alexander Humeniuk ◽  
Merle Insa Silja Röhr
Keyword(s):  
Electronic Properties ◽  
Molecular Packing ◽  
Photovoltaic Devices ◽  
Singlet Fission ◽  
Adiabatic State

Singlet fission has the potential to increase the efficiency of photovoltaic devices, but the design of suitable chromophores is notoriously difficult. Both the electronic properties of the monomer and the...

scholarly journals Indirect bandgap, optoelectronic properties, and photoelectrochemical characteristics of high-purity Ta3N5 photoelectrodes

2021 ◽  
Vol 9 (36) ◽  
pp. 20653-20663
Author(s):  
Johanna Eichhorn ◽  
Simon P. Lechner ◽  
Chang-Ming Jiang ◽  
Giulia Folchi Heunecke ◽  
Frans Munnik ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Electronic Properties ◽  
High Purity ◽  
Optoelectronic Properties ◽  
Precise Control ◽  
Insight Into

The (opto)electronic properties of Ta3N5 photoelectrodes are often dominated by defects, but precise control of these defects provides new insight into the electronic structure, photocarrier transport, and photoelectrochemical function.

scholarly journals Synthesis and Optoelectronic Properties of Iptycene–Naphthazarin Dyes

Synlett ◽  
2018 ◽  
Vol 30 (01) ◽  
pp. 54-58 ◽  
Author(s):  
Timothy Swager ◽  
Cagatay Dengiz ◽  
You-Chi Wu
Keyword(s):  
Single Crystal ◽  
Electronic Properties ◽  
Diels Alder ◽  
Optoelectronic Properties ◽  
Synthesis And Characterization ◽  
Nmr Analysis ◽  
X Ray ◽  
Vis Spectroscopy

We report the synthesis and characterization of iptycene–naphthazarin dyes by using a sequential Diels–Alder approach. The tautomerization of naphthazarin was used as the key step in the synthesis, with structures confirmed by single-crystal X-ray and NMR analysis. The systematic trends in electronic properties were investigated by UV/Vis spectroscopy. BF2 complexes of the dyes were prepared by reaction with BF3·OEt2 in CH2Cl2.

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