Revealing the Charge‐Transfer Interactions in Self‐Assembled Organic Cocrystals: Two‐Dimensional Photonic Applications

Zhu, Weigang; Zheng, Ren-Hui; Fu, Xiaolong; Fu, Hongbing; Shi, Qiang; Zhen, Yonggang; Dong, Huanli; Hu, Wenping

doi:10.1002/anie.201501414

Cited by 216 publications

(186 citation statements)

References 45 publications

Supporting

Mentioning

164

Contrasting

Unclassified

Order By: Relevance

“…Although co-crystals of APIs are not going to be a panacea [for example, it seems unlikely that they will, in general, be any less prone to polymorphism than are homomeric molecular solids (Aitipamula et al, 2014)], they will likely offer useful strategies and opportunities that can facilitate the development of new drugs and formulations for the future. Similar progress can be expected in areas related to agrochemicals (George et al, 2013), nutraceuticals (Schultheiss et al, 2010), liquid crystals (Nguyen et al, 2004), charge-transfer (Zhu et al, 2015) and non-linear optical materials (Gryl et al, 2015), to name but a few.…”

Section: Applications Of Co-crystals and Co-crystal Technologysupporting

confidence: 55%

Is there any point in making co-crystals?

Aakeröy

2015

Acta Crystallogr Sect B

View full text Add to dashboard Cite

show abstract

Section: Applications Of Co-crystals and Co-crystal Technologysupporting

confidence: 55%

Is there any point in making co-crystals?

Aakeröy

2015

Acta Crystallogr Sect B

View full text Add to dashboard Cite

show abstract

“…In contrast the notorious aggregation-caused quenching (ACQ), branchy and twisted aggregation-induced emission (AIE) and aggregation-induced emission enhancement (AIEE) fluorogens are developed to tune the intermolecular stacking for efficient emissions in the solid state29303132. Alternative ways to regulate multifunctional materials are allomorphism and mischcrystal333435. This strategy do not involves tedious organic synthesis.…”

mentioning

confidence: 99%

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Zhang

Kong

et al. 2016

Sci Rep

View full text Add to dashboard Cite

Molecular packing arrangements play a key role in dominating the photophysical properties of luminophores in aggregated state but fine control of the molecular packing is a great challenge. This article describes a unique cyano substituted styrene pyridinium with interesting solid-state fluorescence that can be finely tuned by simple change of counteranions. The dilute solutions of the organic salts (PyCl, PyNO3, PyOTs and PyPh4B) exhibit very weak fluorescence. The crystals of the organic salts (PyCl, PyNO3, and PyOTs) show much enhanced fluorescence compared with their dilute solutions. It is interesting that the emissions changed from bluish-green to deep-blue and fluorescence quantum yields increase from 2.5% to 13.1% with the increasing of steric hindrance of the anions from chloridion, nitrate, to p-toluenesulfonate. Crystal and DFT studies reveal that the enhanced fluorescence is ascribed to the formation of dimers and bigger anions induce larger molecular separation in dimers. Tetraphenylboron anion with very large steric hindrance impedes the formation of dimers and thus results in non-fluorescent salt (PyPh4B). Meanwhile, this unique dimeric packing endows the crystal of PyNO3 with anisotropic fluorescence.

show abstract

“…A puzzle we are encountering is to distinguish the ground and excited state [36,37]. Recently, we [38] found that both of ground and excited states of 1,2,4,5-tetracyanobenzene (TCNB) based cocrystals are actually CT state, as experimentally verified by spectroscopic studies, electron spin resonance (ESR) measurements and theoretical calculations (Fig. 2).…”

Section: Science China Materialsmentioning

confidence: 85%

Challenges of organic “cocrystals”

et al. 2015

Self Cite

View full text Add to dashboard Cite

ly pack in a DAD A···DADA fashion with sufficient D-A π-electron overlap, ii) segregated-stacking, wherein molecules pack in a DDDD···AAAA fashion with D-D and A-A π-overlap.As a novel research area, there are full of challenges for organic cocrystals. The first challenge is the basic mechanism of co-crystallization, because not any two types of materials can recognize each other and self-assemble into a cocrystal. Hence, a question is what kind of material is suitable for co-crystallization, and how different molecules co-assemble, nucleate and crystallize. This is also related to the method applied for co-crystallization, including solution [24], vapor-phase [6,27−29] and mechanochemical techniques [16,30]. In our experience, some fundamental conditions are also essential for solution co-crystallization, such as strong intermolecular interactions, planar molecular structure and similar solubility of donor (D) and acceptor (A). In order to reveal the nucleation and growth mechanism of organic cocrystals and further control the self-assembling process of co-crystallization, we used perylene-tetracyanoquinodimethane (TCNQ) CT cocrystal as an example [31], and found that the morphology and phase of cocrystals mainly depend on the concentration of perylene (C perylene ) rather than TCNQ (C TCNQ ), and high C perylene is favourable for the formation of (perylene) 3 TCNQ (P3T1) microblocks, while low C perylene faciliates the formation of (perylene) 1 TCNQ (P1T1) nanowires (Fig. 1). More importantly, we demonstrate that the formed D-A complex is regarded as a new material species, because the solubility of the formed P3T1 in acetonitrile is obviously lowered than that of any single components. It actually allows us to define the cocrystal as a new molecular species. The structure-function relationship of these cocrystals is further investigated. P1T1 cocrystals exhibit n-type behavior with electron mobility of 0.05 cm 2 V −1 s −1 , while P3T1 cocrystals display ambipolar behavior with high hole mobility of 0.03 cm 2 V −1 s −1 and low electron mobility of 2.1×10 −5 cm 2 V −1 s −1 . Moreover, white light responsivity of P1T1 is higher than Organic cocrystal (also "co-crystal"), formed with two or more different components via non-covalent intermolecular interactions, possesses novel, unpredicted and unique properties, which are not the simple sum of those molecular components, e.g., with effect of 1+1>2. In this regard, organic cocrystals provide a distinctive strategy for the synthesis of novel multifunctional materials, and an important platform for exploring new fundamental physicochemical phenomena in molecular systems, such as high conductivity [1,2] Probably, the first cocrystal could be tracked back to 1844 assigning to the discovery of "quinhydrone" by WÖhler [17], while the conception of "cocrystal" was firstly used by Schmidt and Snipes [18] to describe the crystal of pyrimidine and purine complex in 1967. However, the widely acceptance of this concept is still progressing, since the definition of a cocrysta...

show abstract

Revealing the Charge‐Transfer Interactions in Self‐Assembled Organic Cocrystals: Two‐Dimensional Photonic Applications

Cited by 216 publications

References 45 publications

Is there any point in making co-crystals?

Is there any point in making co-crystals?

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Challenges of organic “cocrystals”

Contact Info

Product

Resources

About