Recent Developments of Photodeformable Polymers: From Materials to Applications.

Photodeformable polymer materials have a far influence in the fields of flexibility and intelligence. The stimulation energy is converted into mechanical energy through molecular synergy. Among kinds of photodeformable polymer materials, liquid crystalline polymer (LCP) photodeformable materials have been a hot topic in recent years. Chromophores such as azobenzene, α-cyanostilbene, and 9,10-dithiopheneanthracene have been widely used in LCP, which are helpful for designing functional molecules to increase the penetration depth of light to change physical properties. Due to the various applications of photodeformable polymer materials, there are many excellent reports in intelligent field. In this review, we have systematized LCP containing azobenzene into 3 categories depending on the degree of crosslinking liquid crystalline elastomers, liquid crystalline networks, and linear LCPs. Other structural, typical polymer materials and their applications are discussed. Current issues faced and future directions to be developed for photodeformable polymer materials are also summarized.

The methylation effect in prolonging the pure organic room temperature phosphorescence lifetime.

Prolonging the phosphorescence lifetime of pure organic phosphorescent materials by a methyl-substitution strategy is described. We present a chemical strategy for improving the phosphorescence lifetime of triplet excitons under ambient conditions by incorporating methyl groups into the chemical structures. This is observed by a long-lived phosphorescence lifetime of up to 0.83 s detected for methylated 9-(4-(mesitylsulfonyl)phenyl)-9H-carbazole (3M), compared to 0.36 s for 9-(4-(phenylsulfonyl)phenyl)-9H-carbazole (0M) without any methyl groups. Additionally, enhanced phosphorescence efficiency can be obtained at an appropriate methylation degree, because of the smaller ΔE ST (singlet and triplet energy gap) and ΔE TT* (normal phosphorescence and long-lived phosphorescence energy gap). A comprehensive investigation on the packing mode in the crystalline state reveals that the methyl groups occupy the free volume and result in a suppression of non-radiative decay, accounting for the enhanced phosphorescence lifetime.

Weak interactions but potent effect: tunable mechanoluminescence by adjusting intermolecular C-H···π interactions.

A new mechanoluminescent material (4-(diphenylamino)phenyl)(4-(diphenylphosphanyl)phenyl)methanone (CDpP), which displays tunable mechanoluminescent emission colors, has been designed and successfully synthesized. CDpP shows two distinct mechanoluminescent colors (blue and green) in different crystalline states. Single-crystal analyses and femtosecond transient emission studies reveal that the striking tunable mechanoluminescence properties of CDpP mainly originate from the different C-H···π interactions in the crystal structures. CDpP crystals with more C-H···π interactions show blue mechanoluminescence (ML), and the emission is attributed to the locally excited (LE)-state because the twisting process for the excited state is restricted by C-H···π interactions. Conversely, CDpP crystals with fewer C-H···π interactions display green ML, in which the red-shifted emission band originates from the twisted intramolecular charge transfer (TICT) excited state because the diphenylamine moiety is relatively free to rotate. The manipulation of weak intermolecular interactions in the crystalline state is a useful and reliable strategy for the tuning of the ML emission wavelengths.

Organic Mechanoluminescence with Aggregation-Induced Emission.

Mechanoluminescence (ML) involves the emission of light from various organic and inorganic materials upon mechanical stimulus. In this review, we contemplate the advances of metal-free, purely organic ML compounds with aggregation-induced emission (AIE), which give strong emission upon mechanical force. We show the new ML-AIE based materials can be used explore the basic of ML properties with structure-property relationships and molecular interactions. The flourishing idea of ML-AIE may help to find the characteristic and elusive component of ML as it partners with AIE, which upgrades the emission property in solids or aggregates. Recent advances in ML-AIE information could increase the wide scope of research in this expanding area, as these materials have promising applications in different optoelectronic areas.

Gated photochromic molecules with AIEgen: turn-on the photochromism with an oxidation reagent.

A couple of gated photochromic molecules TrPEP and TrPEPO with AIEgen have been rationally designed and synthesized. No photochromism is detected for TrPEP whilst TrPEPO shows obvious photochromic properties in the solution state. By adding equimolar H2O2 aqueous solution to the TrPEP solution, the photochromic properties would be quickly turned on. The oxidation reagent acts as a gate to switch the photochromic properties by switching the triphenylphosphine group to a triphenylphosphine oxide group. Both TrPE and TrPEO display typical AIE phenomena. Different intensive emission bands with the emission maxima of 500 nm and 455 nm are detected before (TrPEP) and after (TrPEPO) oxidization in solid states. Combining the AIEgens, photochromic ON/OFF states can be easily indicated by the different emission colors in the solid state. Single crystal analyses and TD-DFT calculations were carried out to further investigate the photophysical and photochromic properties of these compounds. These new triphenylethylene derivatives provide a new strategy to achieve gated photochromic materials with simple chemical structures and gate indicators.