Copper(I)‒Pyrazolate Complexes as Solid-State Phosphors: Deep-

Blue Emission Through a Remote Steric Effect (original) (raw)

Abstract

We describe a novel manifestation of rigidochromic behavior in a series of tetranuclear Cu(I)–pyrazolate (Cu4pz4) macrocycles, with implications for solid-state luminescence at deep-blue wavelengths (<460 nm). The Cu4pz4 emissions are remarkably sensitive to structural effects far from the luminescent core: when 3,5-di-tert-butylpyrazoles are used as bridging ligands, adding a C4 substituent can induce a blue shift of more than 100 nm. X-ray crystal and computational analyses reveal that C4 units influence the conformational behavior of adjacent tert-butyl groups, with a subsequent impact on the global conformation of the Cu4pz4 complex. Emissions are mediated primarily through a cluster-centered triplet (3CC) state; compression of the Cu4 cluster into a nearly close-packed geometry prevents the reorganization of its excited-state structure and preserves the 3CC energy at a high level. The remote steric effect may thus offer alternative strategies toward the design of phosphors with rigid excited-state geometries.

Date of this Version

5-20-2022

Watanabe, Yuichiro; Washer, Benjamin M.; Zeller, Matthias; Savikhin, Sergei; Slipchenko, Lyudmila V.; and Wei, Alexander, "Copper(I)‒Pyrazolate Complexes as Solid-State Phosphors: Deep- Blue Emission Through a Remote Steric Effect" (2022). Department of Chemistry Faculty Publications. Paper 21.
https://docs.lib.purdue.edu/chempubs/21

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