Blue Phosphors of Dinuclear and Mononuclear Copper(I) and Silver(I) Complexes of 3,5-Bis(trifluoromethyl)pyrazolate and the Related Bis(pyrazolyl)borate

Abstract

The synthesis, structure, and photoluminescence properties are described for the three-coordinate mononuclear and dinuclear complexes [H(2)B(3,5-(CF(3))(2)Pz)(2)]M(2,4,6-collidine), M(1)(), and [[3,5-(CF(3))(2)Pz]M(2,4,6-collidine)](2), M(2)(), respectively (M = Cu; Ag). The solids exhibit bright blue phosphorescence, at room temperature for the copper compounds and at 77 K for all compounds. Ag(1)(), Cu(1)(), and Cu(2)() exhibit blue pyrazole-based structured emissions with short phosphorescence lifetimes, 10(1)-10(2) micros, due to an internal heavy-metal effect. Meanwhile, Ag(2)() exhibits curious multiple excitation-dependent emissions.

Phosphorescence sensitization via heavy-atom effects in d10 complexes

“…That is, coordination essentially ''lights up'' the organic ligand! This situation is similar to the mononuclear and dinuclear copper and silver complexes in which the pyrazolate ligand triplet was enhanced irrespective of metal identity [20]. a well resolved structured band dominates with long lifetime, consistent with the triplet of the free ligand.…”

“…An example illustrating this behavior is shown in Fig. 10 [20]. The compounds are brightly phosphorescent at 77 K for all compounds and at room temperature for the copper compounds.…”

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

“…The blue, high-energy emission at 470 nm, associated with the high-energy excitation (320-400 nm), is tentatively attributed to emissive states derived from pyrazolate-to-silver (or cluster) . [63] Unlike the hexanuclear complexes 2 and 3, the related…”

“…[52,55] Apart from the interest arising from their structural diversity, some of these pyrazolate bridging complexes have also been shown to be excellent systems for examining metallophilic interactions [49,[56][57][58][59][60][61][62] and as luminescent materials. [49,[56][57][58][59][63][64][65][66] One of the synthetic strategies used to obtain the above-mentioned heteropolynuclear pyrazolate complexes is the replacement of the proton in coordinated pyrazoles by the metal ions: Cu I , Ag I , and Au I . The self-assembly of the resulting units gives the heterometallic clusters.…”

Effect of Conformation and Combination of 1,3‐Bis(4‐pyridylthio)propan‐2‐one upon Coordination Architectures: Syntheses, Characterizations and Properties

“…The emission properties of 3 are complicated and very interesting. Although several Ag I polymers that emit photoluminescence at room temperature have been reported, [46][47][48][49] complex 3 shows, unusually, multiple emission bands. When excited at 365 nm, it displays two weaker blue emission bands at λ max = 416 and 442 nm and one stronger, broad, green emission band at λ max = 541 nm.…”