Relativistic modulation of supramolecular halogen/copper interactions and phosphorescence in Cu(i) pyrazolate cyclotrimers

Abstract

Described herein is the synthesis, structure, and photophysics of the iodo-substituted cyclic, trinuclear copper(I) complex, Cu3[4-I-3,5-(CF3)2Pz]3 supported by a highly fluorinated pyrazolate and a detailed comparisons to its previously-reported 4-Br/4-Cl...

Ligand-Directed Metalation of a Gold Pyrazolate Cluster

“…This resembles the orange emission shown by solutions of [Au 4 (pz tBu2 ) 4 ] (Hpz tBu2 = 3,5di(tertbutyl)-1H-pyrazole), 46 which arises from metal-to-metal charge transfer (MMCT) transitions within the metallophilic Au•••Au orbital manifold. 12,13,33,47 The emission spectrum of 2 (λ ex = 250 nm) resembles that of 1, but the main visible emission is slightly red-shifted at λ max = 667 nm. The spectrum also has weak additional features in the visible region which may be vibrational structure on the emission bands, reflecting the greater conformational rigidity of 2.…”

“…These are essentially planar, notwithstanding any peripheral substituents, and often aggregate in the crystal through short M···M contacts. Such compounds can show an intense, temperature-dependent emission in the solid state, − from transitions within the intermolecular metallophilic orbitals. − Similarly, hybrid or soft materials based on [M 3 (μ-pz) 3 ] centers can show switchable emission mediated by reversible supramolecular aggregation processes. − Triangular [M 3 (μ-pz) 3 ] centers with appropriate substituents can be π-acid hosts for aromatic guest species, ,,, and D 3 h -symmetric synthons in crystalline frameworks , and in 2D coordination nanosheets …”