Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Enhancing electron affinity and tuning band gap in donor-acceptor organic semiconductors by benzothiadiazole directed C-H borylation.

ABSTRACT: Electrophilic borylation using BCl3 and benzothiadiazole to direct the C-H functionalisation of an adjacent aromatic unit produces fused boracyclic materials with minimally changed HOMO energy levels but significantly reduced LUMO energy levels. In situ alkylation and arylation at boron using Al(alkyl)3 or Zn(aryl)2 is facile and affords boracycles that possess excellent stability towards protic solvents, including water, and display large bathochromic shifts leading to far red/NIR emission in the solid state with quantum yields of up to 34%. Solution fabricated OLEDs with far red/NIR electroluminescence are reported with EQEs > 0.4%.

SUBMITTER: Crossley DL

PROVIDER: S-EPMC5666683 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Enhancing electron affinity and tuning band gap in donor-acceptor organic semiconductors by benzothiadiazole directed C-H borylation.

Crossley D L DL Cade I A IA Clark E R ER Escande A A Humphries M J MJ King S M SM Vitorica-Yrezabal I I Ingleson M J MJ Turner M L ML

Chemical science 20150612 9

Electrophilic borylation using BCl3 and benzothiadiazole to direct the C-H functionalisation of an adjacent aromatic unit produces fused boracyclic materials with minimally changed HOMO energy levels but significantly reduced LUMO energy levels. In situ alkylation and arylation at boron using Al(alkyl)3 or Zn(aryl)2 is facile and affords boracycles that possess excellent stability towards protic solvents, including water, and display large bathochromic shi ...[more]

PMID: 29142733

Similar Datasets

C-H Borylation/Cross-Coupling Forms Twisted Donor-Acceptor Compounds Exhibiting Donor-Dependent Delayed Emission.

Project description:Benzothiadiazole (BT) directed C-H borylation using BCl3 , followed by B-Cl hydrolysis and Suzuki-Miyaura cross-coupling enables facile access to twisted donor-acceptor compounds. A subsequent second C-H borylation step provides, on arylation of boron, access to borylated highly twisted D-A compounds with a reduced bandgap, or on B-Cl hydrolysis/cross-coupling to twisted D-A-D compounds. Photophysical studies revealed that in this series there is long lifetime emission only when the donor is triphenylamine. Computational studies indicated that the key factor in observing the donor dependent long lifetime emission is the energy gap between the S1 /T2 excited states, which are predominantly intramolecular charge-transfer states, and the T1 excited state, which is predominantly a local excited state on the BT acceptor moiety.

| S-EPMC6099339 | biostudies-literature

Hydrogen production by tuning the photonic band gap with the electronic band gap of TiO?.

Project description:Tuning the photonic band gap (PBG) to the electronic band gap (EBG) of Au/TiO2 catalysts resulted in considerable enhancement of the photocatalytic water splitting to hydrogen under direct sunlight. Au/TiO2 (PBG-357 nm) photocatalyst exhibited superior photocatalytic performance under both UV and sunlight compared to the Au/TiO2 (PBG-585 nm) photocatalyst and both are higher than Au/TiO2 without the 3 dimensionally ordered macro-porous structure materials. The very high photocatalytic activity is attributed to suppression of a fraction of electron-hole recombination route due to the co-incidence of the PBG with the EBG of TiO2 These materials that maintain their activity with very small amount of sacrificial agents (down to 0.5 vol.% of ethanol) are poised to find direct applications because of their high activity, low cost of the process, simplicity and stability.

| S-EPMC3794377 | biostudies-literature

Low Band Gap Donor⁻Acceptor Type Polymers Containing 2,3-Bis(4-(decyloxy)phenyl)pyrido[4,3-b]pyrazine as Acceptor and Different Thiophene Derivatives as Donors.

Project description:Four donor⁻acceptor type conducting polymers, namely poly(2,3-bis(4-decyloxy)phenyl)-5,8-bis(4-thiophen-2-yl)pyrido[4,3-b]pyrazine) (P1), poly(2,3-bis(4-decyloxy)phenyl)-5,8-bis(4-butylthiophen-2-yl)pyrido[4,3-b]pyrazine) (P2), poly(2,3-bis(4-(decyloxy)phenyl)-5,8-bis(4-hexyloxythiophen-2-yl)pyrido[4,3-b]pyrazine) (P3) and poly(2,3-bis(4-(decyloxy)phenyl)-5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)pyrido[4,3-b]pyrazine) (P4), containing thiophene or its derivative as the donor and pyrido[4,3-b]pyrazine as the acceptor were prepared and characterized by cyclic voltammetry, scanning electron microscopy, and UV-Vis spectroscopy to detect the influence of the donor units' strength on the electrochromic performances. The results demonstrated that all of the polymers could be reversibly reduced and oxidized by p-type doping and n-type doping, and showed near-infrared activities and different color changes in p-type doping process. Especially, P3 and P4 showed lower optical band gap than P1 and P2 due to the strong electron-donating hexyloxythiophen group of P3 and ethylenedioxythiophene group of P4. Besides, P3 and P4 displayed the saturated green color at the neutral state and the desirable transparency at the oxidized state. All the polymers displayed desirable optical contrasts, satisfactory coloration efficiency, excellent stability and short switching time, which made the polymers fascinating candidates in the electrochromic device applications.

| S-EPMC6432059 | biostudies-literature

Highly Emissive Far Red/Near-IR Fluorophores Based on Borylated Fluorene-Benzothiadiazole Donor-Acceptor Materials.

Project description:Stille, Suzuki-Miyaura and Negishi cross-coupling reactions of bromine-functionalised borylated precursors enable the facile, high yielding, synthesis of borylated donor-acceptor materials that contain electron-rich aromatic units and/or extended effective conjugation lengths. These materials have large Stokes shifts, low LUMO energies, small band-gaps and significant fluorescence emission >700 nm in solution and when dispersed in a host polymer.

| S-EPMC6680280 | biostudies-literature

Triplet excited state properties in variable gap ?-conjugated donor-acceptor-donor chromophores.

Project description:A series of variable band-gap donor-acceptor-donor (DAD) chromophores capped with platinum(ii) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet-triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin-orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

| S-EPMC6008705 | biostudies-other

Controlling n-Type Molecular Doping via Regiochemistry and Polarity of Pendant Groups on Low Band Gap Donor-Acceptor Copolymers.

Project description:We demonstrate the impact of the type and position of pendant groups on the n-doping of low-band gap donor-acceptor (D-A) copolymers. Polar glycol ether groups simultaneously increase the electron affinities of D-A copolymers and improve the host/dopant miscibility compared to nonpolar alkyl groups, improving the doping efficiency by a factor of over 40. The bulk mobility of the doped films increases with the fraction of polar groups, leading to a best conductivity of 0.08 S cm-1 and power factor (PF) of 0.24 μW m-1 K-2 in the doped copolymer with the polar pendant groups on both the D and A moieties. We used spatially resolved absorption spectroscopy to relate commensurate morphological changes to the dispersion of dopants and to the relative local doping efficiency, demonstrating a direct relationship between the morphology of the polymer phase, the solvation of the molecular dopant, and the electrical properties of doped films. Our work offers fundamental new insights into the influence of the physical properties of pendant chains on the molecular doping process, which should be generalizable to any molecularly doped polymer films.

| S-EPMC8154869 | biostudies-literature

Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors.

Project description:Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8?cm(2)V(-1)s(-1)), on/off ratio (10(7)), and other desirable field-effect properties that meet impactful OFET application requirements.

| S-EPMC4835732 | biostudies-literature

Electronically Driven Regioselective Iridium-Catalyzed C-H Borylation of Donor-?-Acceptor Chromophores Containing Triarylboron Acceptors.

Project description:We observed a surprisingly high electronically driven regioselectivity for the iridium-catalyzed C-H borylation of donor-?-acceptor (D-?-A) systems with diphenylamino (1) or carbazolyl (2) moieties as the donor, bis(2,6-bis(trifluoromethyl)phenyl)boryl (B(F Xyl)2 ) as the acceptor, and 1,4-phenylene as the ?-bridge. Under our conditions, borylation was observed only at the sterically least encumbered para-positions of the acceptor group. As boronate esters are versatile building blocks for organic synthesis (C-C coupling, functional group transformations) the C-H borylation represents a simple potential method for post-functionalization by which electronic or other properties of D-?-A systems can be fine-tuned for specific applications. The photophysical and electrochemical properties of the borylated (1-(Bpin)2 ) and unborylated (1) diphenylamino-substituted D-?-A systems were investigated. Interestingly, the borylated derivative exhibits coordination of THF to the boronate ester moieties, influencing the photophysical properties and exemplifying the non-innocence of boronate esters.

| S-EPMC7497074 | biostudies-literature

Effects of Fluoro Substitution on the Electrochromic Performance of Alternating Benzotriazole and Benzothiadiazole-Based Donor⁻Acceptor Type Copolymers.

Project description:Two new donor⁻acceptor type electrochromic copolymers containing non-fluorinated and di-fluorinated benzothiadiazole analogues, namely P(TBT-TBTh) and P(TBT-F-TBTh), were synthesized successfully through chemical polymerization. Both polymers were measured by cyclic voltammetry, UV-vis spectroscopy, colorimetry and thermogravimetric analysis to study the influence of fluoro substitution on the electrochromic performance. The results demonstrated that the two polymer films displayed well-defined redox peaks in pairs during the p-type doping, and showed distinct color change from dark gray blue to light green for P(TBT-TBTh) with the band gap of 1.51 eV, and from gray blue to celandine green for P(TBT-F-TBTh) with the band gap of 1.58 eV. P(TBT-F-TBTh) presented lower highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, and better stability than P(TBT-TBTh). It was found that the two fluorine atoms participated in not only inductive effects but also mesomeric effects in the P(TBT-F-TBTh) backbone. In addition, the polymers exhibited high optical contrasts, short response time, and favorable coloration efficiency, especially in the near infrared region. The characterization results indicated that the two reported polymers can be the potential choice as electrochromic materials.

| S-EPMC6414881 | biostudies-other

Effect of electronic acceptor segments on photophysical properties of low-band-gap ambipolar polymers.

Project description:Stimulated by a recent experimental report, charge transfer and photophysical properties of donor-acceptor ambipolar polymer were studied with the quantum chemistry calculation and the developed 3D charge difference density method. The effects of electronic acceptor strength on the structure, energy levels, electron density distribution, ionization potentials, and electron affinities were also obtained to estimate the transporting ability of hole and electron. With the developed 3D charge difference density, one visualizes the charge transfer process, distinguishes the role of molecular units, and finds the relationship between the role of DPP and excitation energy for the three polymers during photo-excitation.

| S-EPMC3556892 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data