Understanding AIE and ACQ phenomenon of organometallic iridium(Ⅲ) complexes by simple cationization engineering

Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF_(6)] with two counterions is obtained by simple Nmethylation of the ancillary ligand of [Ir1-f][PF_(6)] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders.[Ir1-f][PF_(6)] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission(AIE) activity. On the sharp contrary, [Ir2-f][2PF_(6)] is an aggregation-caused quenching(ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF_(6)] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.

Rational design of an AIE-active metal-organic framework for highly sensitive and portable sensing nitroaromatic explosives

Herein,we report a new metal-organic framework with an AIE ligand (H_(4)TCPP=2,3,5,6-tetra-(4-carboxyphenyl)pyrazine) and Mg^(2+) ions,that is,[Mg_(2)(H_(2)O)_(4)TCPP]·DMF·5CH_(3)CN (Mg-TCPP,TCPP=tetra-(4-carboxyphenyl)pyrazine) for detection of nitroaromatic explosives.Due to the coordination effect and restricted intramolecular rotation,Mg-TCPP exhibits bright blue light.As a fluorescent sensor,Mg-TCPP exhibits high selectivity and sensitivity for sensing 2,4,6-trinitrophenol (TNP) by quenching behaviors with the Stern-Volmer quenching constant (K_(SV)) of 3.63×10^(5)L/mol and achieves the low limit of detection of 25.6 ppb,which is beyond most of the previously reported fluorescent materials.Notably,the portable Mg-TCPP films are prepared and it can be used for rapid and sensitive TNP detection in a variety of environments including organic solvent and aqueous solution.Moreover,TNP vapor can be detected within 3 min by naked eye and the film could be regenerated under simple solvent cleaning.

Rational design of AIE-active biodegradable polycarbonates for high-performance WLED and selective detection of nitroaromatic explosives

Luminescent polymers have garnered considerable research attention for their excellent properties and wide range of applications in multi-responsive materials,bioimaging,and photoelectric devices.Thereout,various modulations of polymer structure are often the main approach to obtaining materials with different luminescent colors and functions.However,polymers with biodegradability,tunable color,and efficient emission simultaneously remain a challenge.Herein,we report a feasible strategy to achieve degradable and highly emissive polymers by exquisite combination and interplay of aggregation-induced emission(AIE)unit and environmental-friendly epoxide/CO_(2)copolymerization.A series of polycarbonates P-TEP_(x)CN_(y)(x=0,1,2,4,30,120;y=0,1)were prepared,with emission color changed from blue to yellow by controlling the proportion of two designed AIE-active monomers.Among them,Using P-TCN as emitting layer,high performance white light-emitting diode(WLED)device with an external quantum efficiency(EQE)of 26.09%and CIE coordinates of(0.32,0.32)was achieved.In addition,the designed polymers can be used as selective sensors for nitroaromatic compounds in their nanoaggregate states.