A Soluble Dynamic Complex Strategy for the Solution‐Processed Fabrication of Organic Thin‐Film Transistors of a Boron‐Containing Polycyclic Aromatic Hydrocarbon

Matsuo, Kyohei; Saito, Shohei; Yamaguchi, Shigehiro

doi:10.1002/ange.201605221

Cited by 16 publications

(4 citation statements)

References 84 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, Yamaguchi and co-workers observed this in a pyridine adduct of a partially fused trinaphthylborane (Chart 2), which resulted in the presence of two different emissive species in solution. 39,44 Pammer reported on the photodissociation of B−N intramolecular dative bonds ladder boranes. 45 Tanaka and Chujo observed dual emissions from borafluorenes with intramolecular amine coordination (Chart 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Boranes with Ultra-High Stokes Shift Fluorescence

et al. 2018

View full text Add to dashboard Cite

The synthesis and optical characterization of 9-(2,6bis(methoxymethyl)phenyl) borafluorene (BMMP-BF) are reported. NMR spectroscopic data and single-crystal X-ray diffraction data of BMMP-BF show intramolecular chelation by the 2,6-bis(methoxymethyl)phenyl moiety via a boron−oxygen dative bond. The optical spectra of BMMP-BF are unusual in that absorption is entirely in the UV region (λ max = 284 nm), yet fluorescence occurs at 536 nm. This equates to a Stokes shift of 2.05 eV (16 500 cm −1 ) and is among the highest Stokes shifts ever reported for a small molecule. Density functional theory (DFT) calculations show that the boron−oxygen dative bond in BMMP-BF is ruptured in the excited state and that emission occurs from a trigonal planar boron geometry. This bond cleavage and the concurrent planarization of the boron center are responsible for the high Stokes shift. Two borafluorenes related to BMMP-BF were also examined: 9-(2,6-bis((methylthio)methyl)phenyl) borafluorene (BMTMP-BF) and 9-(2,6-bis(tert-butoxymethyl)phenyl) borafluorene (B t BuMP-BF). Both BMTMP-BF and B t BuMP-BF have optical properties similar to those of BMMP-BF with remarkably large Stokes shifts. Finally, BMMP-BF-(2T) 2 , which possesses bithiophene moieties on the 2 and 7 positions of a BMMP-BF core, was also synthesized and studied. The absorption spectrum of BMMP-BF-(2T) 2 is red-shifted compared to BMMP-BF. BMMP-BF-(2T) 2 was found to exhibit dual emissions rather than the single, high Stokes shift emission of BMMP-BF. DFT calculations suggest that the dual emissions of BMMP-BF-(2T) 2 arise due to radiative relaxation from two different structures in the excited state.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Boranes with Ultra-High Stokes Shift Fluorescence

et al. 2018

View full text Add to dashboard Cite

show abstract

“…The coordination/dissociation dynamics of B−N Lewis adduct was particularly useful to produce semiconducting films of PAH-based materials. 149 Just like many other PAHs, 25a suffers from poor solubility in most common organic solvents including chloroform, toluene, and chlorobenzene. In the presence of a small amount of pyridine, the solubility significantly improved due to the formation of the nonplanar 25a•Py.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Structurally Constrained Boron-, Nitrogen-, Silicon-, and Phosphorus-Centered Polycyclic π-Conjugated Systems

et al. 2019

Self Cite

View full text Add to dashboard Cite

Incorporation of main group elements into the π-conjugated frameworks is a sophisticated strategy to alter the fundamental nature of the parent conjugated πsystems, giving rise to attractive electronic and photophysical properties that are otherwise inaccessible with classic carbon-or metal-based materials. Out of all πconjugated heterocycles, those that are structurally constrained by tethered aryl substituents surrounding the main group center deserve a great deal of attention because not only do they commonly possess the maximum efficiency of π-conjugation and intermolecular interaction, but they also enjoy remarkable thermal and morphological stabilities that are especially crucial for solid-state performances. In certain cases, elucidation of the behavior of such compounds may additionally provide sufficient perspective toward graphene materials doped with main group elements, which are widely considered as potential next-generation optoelectronic materials. In this review, we will specifically focus on historical developments of structurally constrained polycyclic π-electron systems particularly of those with boron, nitrogen, silicon, or phosphorus atoms annulated directly into the center of π-conjugated systems. CONTENTSReview pubs.acs.org/CR

show abstract

“…Notably, single-component deposited films without pyridine could be obtained, as pyridine can be facilely removed under reduced pressure. 58 To investigate the functionality of the prepared supramolecular polymer, work on such thin films is now in progress in our laboratory.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…49,54−57 This labile Lewis acid−base complexation leads to photodissociation behavior in PTAB−pyridine adducts 49 and was also employed for the thin-film formation of poorly soluble materials. 58 However, attempts to utilize this Lewis acidity to control the self-assembly process have not been reported so far.…”

Section: ■ Introductionmentioning

confidence: 99%

Dual Trapping of a Metastable Planarized Triarylborane π-System Based on Folding and Lewis Acid–Base Complexation for Seeded Polymerization

et al. 2021

Self Cite

View full text Add to dashboard Cite

We report the kinetically controlled supramolecular polymerization of boron-containing π-conjugated molecules, which was enabled by a seeding method based on dual trapping of a metastable state by synergistic intramolecular hydrogen bonding and Lewis acid-based complexation. Planarized triarylborane-based 1, which bears a diamide chain with chiral alkyl groups, was synthesized. Upon cooling, the solution of monomer 1 afforded a supramolecular polymerization in a cooperative manner to form helical supramolecular nanostructures with intense J-type aggregate emission. In the presence of pyridine, the triarylborane moiety formed a Lewis acid−base complex, which enhances the stabilization of the metastable monomeric state. An assembly incompetent structure with a folded diamide chain conformation and a pyridine moiety axially coordinated to the boron atom is responsible for slowing the spontaneous aggregation. The seeding method was successfully applied to the solution to produce homogeneous nanofibers even at a high (millimolar-level) concentration. This unprecedented kinetic control via dual trapping provides an effective method to achieve seed-initiated polymerization under concentrated conditions.

show abstract

A Soluble Dynamic Complex Strategy for the Solution‐Processed Fabrication of Organic Thin‐Film Transistors of a Boron‐Containing Polycyclic Aromatic Hydrocarbon

Cited by 16 publications

References 84 publications

Boranes with Ultra-High Stokes Shift Fluorescence

Boranes with Ultra-High Stokes Shift Fluorescence

Structurally Constrained Boron-, Nitrogen-, Silicon-, and Phosphorus-Centered Polycyclic π-Conjugated Systems

Dual Trapping of a Metastable Planarized Triarylborane π-System Based on Folding and Lewis Acid–Base Complexation for Seeded Polymerization

Contact Info

Product

Resources

About