Alam Parvej, Kaur Gurpreet, Chakraborty Shamik, Roy Choudhury Angshuman, Laskar Inamur Rahaman
Department of Chemistry, Birla Institute of Technology and Science, Pilani Campus, Pilani, Rajasthan, India.
Dalton Trans. 2015 Apr 14;44(14):6581-92. doi: 10.1039/c4dt03424d.
On reaction of 2,2'-bipyridine with iridium(iii), an "aggregation induced phosphorescence (AIP)" active "rollover" complex, [Ir(PPh3)2(bipy-H)(Cl)(H)] (bipy-H = κ(2)-N,C-2,2'-bipyridine) or [Ir(bipy-H)], is obtained. The emission colour changes from bluish-green to yellowish-orange and vice versa after repeated protonation and deprotonation of [Ir(bipy-H)], respectively, which unequivocally supports its reversible nature. [Ir(bipy-H)] is sensitive to acids with different pKa values. Tuning of the emission properties can be achieved in the presence of acids with different pKas. This behaviour allows the complex, [Ir(bipy-H)], to function as a phosphorescent acid sensor in both solution and the solid state, as well as a chemosensor for detecting acidic and basic organic vapours. The protonated form, [Ir(bipy-H)H(+)], which is generated after protonation of [Ir(bipy-H)] can be used as a solvatochromic probe for oxygen containing solvents, and also shows vapochromic properties. The emission, absorption and (1)H NMR spectra of [Ir(bipy-H)] under acidic and basic conditions demonstrate its reversible nature. DFT based calculations suggest that changes in the electron affinity of the pyridinyl rings are responsible for all these processes.
2,2'-联吡啶与铱(III)反应时,会得到一种具有“聚集诱导磷光(AIP)”活性的“翻转”配合物,[Ir(PPh3)2(bipy-H)(Cl)(H)](bipy-H = κ(2)-N,C-2,2'-联吡啶)或[Ir(bipy-H)]。[Ir(bipy-H)]在反复质子化和去质子化后,发射颜色分别从蓝绿色变为黄橙色,反之亦然,这明确支持了其可逆性质。[Ir(bipy-H)]对具有不同pKa值的酸敏感。在存在不同pKa的酸时,可以实现发射性质的调节。这种行为使得配合物[Ir(bipy-H)]在溶液和固态中都能作为磷光酸传感器,以及用于检测酸性和碱性有机蒸气的化学传感器。[Ir(bipy-H)]质子化后生成的质子化形式[Ir(bipy-H)H(+)]可作为含氧化合物溶剂的溶剂致变色探针,并且也表现出气相变色性质。[Ir(bipy-H)]在酸性和碱性条件下的发射、吸收和(1)H NMR光谱证明了其可逆性质。基于密度泛函理论(DFT)的计算表明,吡啶基环电子亲和力的变化是所有这些过程的原因。