Diarylfluorenes-based π-stacked molecules: synthesis, X-ray crystallography, and supramolecular light-emitting devices

Yang, Yang; Zhao, Jianfeng; Liu, Ranran; Li, Jiewei; Yi, Moonsuk; Xie, Guohua; Xie, Linghai; Chang, Yong-Zheng; Yin, Changlong; Zhou, X. H.; Zhao, Yi; Qian, Yan; Huang, Wei

doi:10.1016/j.tet.2013.02.090

Cited by 14 publications

(5 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More unexpectedly, under the condition of CF 3 COOH additive, we found that the ratio of meso-DHG1:rac-DHG1 was 7.2:1, which is identical to 75.6% diastereomeric excess (de) of the meso-configuration. Considering the thermodynamic equilibrium of Friedel-Crafts reactions 41 , we prolonged the reaction time and found that the total DHG1 yields were overall reduced from 77% to 55% (Fig. 2c).…”

Section: Resultsmentioning

confidence: 99%

Stereoselective gridization and polygridization with centrosymmetric molecular packing

et al. 2020

Self Cite

View full text Add to dashboard Cite

The gridarenes, with well-defined edges and vertices, represent versatile nanoscale building blocks for the installation of frameworks and architectures but suffer from difficulty in stereoselective control during their synthesis. Here we report a diastereoselective gridization of superelectrophilic diazafluorene-containing substrates (AmBn) with crescent shapes into Drawing Hands grids (DHGs). The meso-selectivity reaches 75.6% diastereomeric excess (de) during the gridization of A1B1-type substrates and maintains ~80% de during the polygridization of A2B2-type monomers. Such stereocontrol originates from the centrosymmetric molecular packing of two charge-delocalized superelectrophiles with synergistically π–π stacking attractions and coulombic repulsions. As meso-stereoregular structures show 20∼30 nm in length, the rigid ring/chain-alternating polygrids have a Mark–Houwink exponent of 1.651 and a molecular weight (M) dependence of the hydrodynamic radius Rh ∼ M1.13. Via the simulation of chain collapse, meso-configured polygridarenes still adopt rod-like conformations that facilitate the high rigidity of organic nanopolymers, distinguished from toroid backbones of rac-type polygrids.

show abstract

Section: Resultsmentioning

confidence: 99%

Stereoselective gridization and polygridization with centrosymmetric molecular packing

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…10 One the one hand, 2,7 or 3,6-position have excellent linkage capility with high-effeciency sp 2 -sp 2 carbon-carbon coupling reaction such as well-known Pd-catalyzed Suzuki reaction; 12 on the other hand, 9,9-position exhibit strong covalent ability via typically multiple modes of -/-, +/+, or -/+ reactions, especially the reaction advantages from excellent BF3•Et2O-mediated Friedel-Crafts (F-C) reaction of fluorenols that belong to C-H reaction mode, occur at the room temperature with high-effeciency and metal-free features 13 and have reversibility at the condition of acids. 14 Ultermiately, unit laddertype 3b (chart 1) and fused digrid grids 3a have made breakthough by means of the fluorenes backbone with the ability of reactive groups that possess potentially well-defined bonding sites and flexible types of linkages.…”

Section: Chart 1 Ladder-like Vs Windmill-like Nanogridsmentioning

confidence: 99%

Organic Nanosynthesis of Ancient Windmill-like Window Gridarenes at Molecular Scale

Wei¹,

Feng²,

H³

et al. 2018

Preprint

Self Cite

View full text Add to dashboard Cite

We focus on another kind of square-type unit nanogrids with starlike divergent extensibility. As a result, square windmill-like nanogrid WG4 have been successfully synthesized by two different kinds of fluorene-based nanosynthons, namely I-shape nanosynthon and L-shape nanosynthon synthesis method. Besides WG4, triangle and hexagon windmill-like nanogrids (WG3 and WG5) are also obtained via one-pot nanosynthesis of I-shape nanosynthon with WG3 as the main product. For the L-shape nanosynthon synthetic method, the cyclization process possesses higher selectivity, resulting to an excellent yield for WG4. In addition, two stereoisomers of the triangle nanogrids, cis-trans-WG3 and cis-cis-WG3, were separated and characterized from the single-crystal X-ray diffraction and 1H NMR analyses for getting insight into the configuration of the triangle nanogrids with the skeleton planarization for the trans-configuration and deplanarization for the cis-configuration.

show abstract

“…Generally, there is the limited alternation of electronic structures but the dramatic change in terms of the intermolecular/supramolecular interaction, 3 molecular packing or nanoscale aggregates, 4 even long range ordering 5 that in-turn dominate the macroscopically statistic exciton and charge behaviors of organic semiconductors. Until now, the typical steric design includes steric hindrance, 6 strain, 7,8 configuration, 9 through-space π-stacks 10,11 as well as attractor-repulsor 12,13 and so on. In the background, it is significant to explore the design of the state-of-the-art steric complex systems that contain the multifactors such as both π-π stacks and strains, serving as the key scaffolds for the design of organic intelligent semiconductors to tune electronic, excitonic and ionic behaviors.…”

Section: Introductionmentioning

confidence: 99%

Strained delta-stacked motifs of nanogridarenes achieved via Pd-PPh3-controlled diastereoselective C-H gridization

Xie

Wei

Huang

et al. 2022

Preprint

Self Cite

View full text Add to dashboard Cite

Strained nanogrids are the hybrids between nanogrids and nanorings with high strain like CPPs, offering state-of-the-art models and versatile nanobricks for advanced materials. Herein, we reported the unique blue-emitting strained triangle windmill-type nanogrids (TWGs) with π-interrupted backbones and delta-stacked motifs that have two diastereoisomers with different strains (cis-trans-TWG 15.60 kcal/mol, cis-cis-TWG 13.31 kcal/mol). They are synthesized by Pd-PPh3-assisted C-H gridization with size-selectivity of TWGs in 35 % yield and diastereoselectivity of cis-trans-TWG/cis-cis-TWG (80:20). Single-crystal X-ray diffraction and non-covalent index reveal both diastereoisomers exhibit the unique angle, bending, torsion as well as steric strains. Among those, torsion strain of cis-trans-TWG is much greater than that of cis-cis-TWG. Furthermore, strain-induced red shift of 25 nm in cis-trans-TWG than cis-cis-TWG was confirmed by TDDFT and photophysics charaterization. Interestingly, aggregates-induced emission switching and enhancement was observed in cis-trans-TWG skeleton with concentration from 10-5 to 10-1.

show abstract

Diarylfluorenes-based π-stacked molecules: synthesis, X-ray crystallography, and supramolecular light-emitting devices

Cited by 14 publications

References 49 publications

Stereoselective gridization and polygridization with centrosymmetric molecular packing

Stereoselective gridization and polygridization with centrosymmetric molecular packing

Organic Nanosynthesis of Ancient Windmill-like Window Gridarenes at Molecular Scale

Strained delta-stacked motifs of nanogridarenes achieved via Pd-PPh3-controlled diastereoselective C-H gridization

Contact Info

Product

Resources

About