Organic molecules exhibiting afterglow emission (lifetime longer than 0.1 s) under ambient conditions have sparked tremendous attention in recent years as a sustainable energy source with potential applications in displays, lighting, and bioimaging. However, white afterglow organic materials with color purity during the entire period of delayed emission, after the cessation of excitation source, are yet to be achieved due to the different excited state lifetimes of its primary or complementary components. Herein, a remarkable, ambient “temporally pure white afterglow,” which lasts for over 7 s, by coorganizing complementary blue and greenish‐yellow organic room temperature phosphors with similar ultralong lifetimes and efficiency, in an amorphous polymer film is demonstrated. One of the most efficient blue afterglow room temperature phosphors is also reported, with an ultralong lifetime up to 2.26 s and maximum quantum efficiency of 36.8%, from purely organic triazatruxenes en route to the realization of this white afterglow. Further, broad and complementary absorption features of the coorganized phosphors in the visible region facilitates an excitation‐dependent dynamic color‐tuning of the afterglow from sky‐blue to greenish‐yellow.
The simple combination of Pd(II) with the tris-monodentate ligand bis(pyridin-3-ylmethyl) pyridine-3,5-dicarboxylate, L, at ratios of 1:2 and 3:4 demonstrated the stoichiometrically controlled exclusive formation of the "spiro-type" Pd1L2 macrocycle, 1, and the quadruple-stranded Pd3L4 cage, 2, respectively. The architecture of 2 is elaborated with two compartments that can accommodate two units of fluoride, chloride, or bromide ions, one in each of the enclosures. However, the entry of iodide is altogether restricted. Complexes 1 and 2 are interconvertible under suitable conditions.
Complexation of 1,4-phenylenebis(methylene) diisonicotinate, L1, with cis-protected Pd(II) components, [Pd(L')(NO3 )2 ], in an equimolar ratio yielded binuclear complexes, 1 a-d of [Pd2 (L')2 (L1)2 ](NO3 )4 formulation where L' stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), and phenanthroline (phen). The combination of 4,4'-bipyridine, L2, with the cis-protected Pd(II) units is known to yield molecular squares, 2 a-d. However, 2 b-d coexist with the corresponding molecular triangles, 3 b-d. Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis-protected Pd(II) components in DMSO resulted in the D-shaped heteroligated complexes [Pd2 (L')2 (L1)(L2)](NO3 )4 , 4 a-d. Two units of the D-shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2 (L')2 (L1)(L2)]2 (NO3 )8 , 5 a-d under aqueous conditions. Crystal structures of the macrocycle [Pd2 (tmeda)2 (L1)(L2)](PF6 )4 , 4 b'', and the catenane [Pd2 (bpy)2 (L1)(L2)]2 (NO3 )8 , 5 c, provide unequivocal support for the proposed molecular architectures.
Bis(pyridin‐3‐ylmethyl) pyridine‐3,5‐dicarboxylate (L) possessing one internal and two terminal pyridine moieties displayed differential coordination ability when combined with suitable PdII components. The compound L acted as a bidentate chelating ligand to form mononuclear complexes when combined with cis‐[Pd(tmeda)(NO3)2] or Pd(NO3)2 in calculated ratios. The combination of Pd(NO3)2 with L in a ratio of 3:4, however, afforded the trinuclear “double‐decker” cage [(NO3)2⊂Pd3(L)4](NO3)4, in which L acts as a nonchelating tridentate ligand and the counter anion (i.e., NO3–) acts as template. The encapsulated NO3– can be replaced by F–, Cl–, or Br– but not by I–. The F–‐encapsulated cage could not be isolated due to its reactivity, whereas the Cl– or Br– encapsulated cages could be isolated. Although anionic guests such as NO3–, Cl–, or Br– stabilized the cages, the presence of excess Cl– or Br– (not NO3–) facilitated decomplexation reactions releasing the ligand. The complexation of Pd(Y)2 (Y = BF4–, PF6–, CF3SO3–, or ClO4–) with L afforded the corresponding mononuclear complexes under appropriate conditions. However, these counter anions could not act as templates for the construction of double‐decker cages.
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