Photosalience and Thermal Phase Transitions of Azobenzene- and Crown Ether-Based Complexes in Polymorphic Crystals

Wang, Chi-Hsien; Lin, Yi-Chia; Bhunia, Surojit; Feng, Yuanning; Kundu, Pramita; Stern, Charlotte L.; Chen, Pei-Lin; Stoddart, J. Fraser; Horie, Masaki

doi:10.1021/jacs.3c06371

Cited by 10 publications

(6 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, it should be noted that the D‐A system based on noncovalent bonding is prone to partial dissolution during photocatalysis, leading to crystal structure destruction. [ 126 ] Therefore, improving the photostability is a problem to be addressed.…”

Section: Intramolecular D‐a Interactionsmentioning

confidence: 99%

Organic Donor‐Acceptor Systems for Photocatalysis

Wang,

Zhu

2023

Advanced Science

View full text Add to dashboard Cite

Organic semiconductor materials are considered to be promising photocatalysts due to their excellent light absorption by chromophores, easy molecular structure tuning, and solution‐processable properties. In particular, donor‐acceptor (D‐A) type organic photocatalytic materials synthesized by introducing D and A units intra‐ or intermolecularly, have made great progress in photocatalytic studies. More and more studies have demonstrated that the D‐A type organic photocatalytic materials combine effective carrier separation, tunable bandgap, and sensitive optoelectronic response, and are considered to be an effective strategy for enhancing light absorption, improving exciton dissociation, and optimizing carrier transport. This review provides a thorough overview of D‐A strategies aimed at optimizing the photocatalytic performance of organic semiconductors. Initially, essential methods for modifying organic photocatalytic materials, such as interface engineering, crystal engineering, and interaction modulation, are briefly discussed. Subsequently, the review delves into various organic photocatalytic materials based on intramolecular and intermolecular D‐A interactions, encompassing small molecules, conjugated polymers, crystalline polymers, supramolecules, and organic heterojunctions. Meanwhile, the energy band structures, exciton dynamics, and redox‐active sites of D‐A type organic photocatalytic materials under different bonding modes are discussed. Finally, the review highlights the advanced applications of organic photocatalystsand outlines prospective challenges and opportunities.

show abstract

Section: Intramolecular D‐a Interactionsmentioning

confidence: 99%

Organic Donor‐Acceptor Systems for Photocatalysis

Wang,

Zhu

2023

Advanced Science

View full text Add to dashboard Cite

show abstract

“…Stimuli-induced solid-state molecular motion and rearrangement form the basis for optical, − mechanical (morphological), − electrical, , and/or topochemical − responses of molecular crystals. A mechanistic understanding of how molecules move within the constraints of crystalline lattices and noncovalent interactions is crucial for the rational design of molecular crystals for use in machinery, sensory devices, and organic electronics.…”

Section: Introductionmentioning

confidence: 99%

Bifurcated Polymorphic Transition and Thermochromic Fluorescence of a Molecular Crystal Involving Three-Dimensional Supramolecular Gear Rotation

Yang,

Chen,

Chuang

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The ability of molecules to move and rearrange in the solid state accounts for the polymorphic transition and stimuliresponsive properties of molecular crystals. However, how the crystal structure determines the molecular motion ability remains poorly understood. Here, we report that a three-dimensional (3D) supramolecular gear network in the green-emissive polymorph 1G of a dialkylamino-substituted anthracene-pentiptycene π-system (1) enables an unusual bifurcated polymorphic transition into a yellow-emissive polymorph (1Y) and a new green-emissive polymorph (1G*) via 3D correlated supramolecular rotation. The 90°forward correlated rotation causes the molecular conformation between the octyl and the anthracene units to change from syn to anti, the ladder-like supramolecular columns to constrict, and the gear network to disengage. This cooperative molecular motion is marked by the gradual formation of an intermediate state (1I) across the entire crystal from 170 to 230 °C, which then undergoes bifurcated (forward or backward rotation) and irreversible transitions to form polymorphs 1Y and 1G* at 230−235 °C. Notably, 1G* is similar to 1G but lacks gear engagement, preventing its transformation into 1Y. Nevertheless, 1G can be restored by grinding 1Y or 1G* or fuming with dichloromethane (DCM) vapor. This work illustrates the correlation between the crystal structure and solid-state molecular motion behavior and demonstrates how a 3D molecular gear system efficiently transmits thermal energy to drive the polymorphic transition and induce fluorochromism through significant conformational and packing changes.

show abstract

“…Azobenzene, a well-known stimuli-responsive molecule, undergoes trans -to- cis isomerization upon photoirradiation, a process reversible by subsequent photoirradiation, heat, or acid . While there are reports on macrocycles containing azobenzene units, π-conjugated macrocycles with three or more azobenzene units remain unexplored.…”

mentioning

confidence: 99%

Tris-Azo Triangular Paraphenylenes: Synthesis and Reversible Interconversion into Radial π-Conjugated Macrocycles

Ide,

Huang,

Horie

2024

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

We report the synthesis of cycloparaphenylene derivatives featuring tris-azo groups. The smaller derivative, [3]cycloazobenzene, adopts a triangular all-cis form and exhibits thermally and photochemically stable characteristics due to significant ring strain as well as symmetric Kagome-patterned crystal packing. In contrast, the as-synthesized [3]cycloazobenzene with three biphenylene bridges adopts a triangular all-cis form, which undergoes photoinduced isomerization, leading to a photostationary state. Interestingly, the addition of an excess of acid selectively leads to the formation of an all-trans form. DFT calculations reveal that the interconversion from a triangular to a circular shape correlates with an increase in HOMO and a decrease in LUMO, characteristics intrinsic to radial π-conjugated systems.

show abstract

Photosalience and Thermal Phase Transitions of Azobenzene- and Crown Ether-Based Complexes in Polymorphic Crystals

Cited by 10 publications

References 50 publications

Organic Donor‐Acceptor Systems for Photocatalysis

Organic Donor‐Acceptor Systems for Photocatalysis

Bifurcated Polymorphic Transition and Thermochromic Fluorescence of a Molecular Crystal Involving Three-Dimensional Supramolecular Gear Rotation

Tris-Azo Triangular Paraphenylenes: Synthesis and Reversible Interconversion into Radial π-Conjugated Macrocycles

Contact Info

Product

Resources

About