Abstract
A new silver(I) iodide cluster [Ag4I4(TMP)4] (TMP = tris(3-methylphenyl)-phosphine) 1 shows triply stimuli-responsive luminescent chromism, namely, mechano-, thermo- and solvent-responsive chromism, which is isostructural to our previously reported [Cu4I4(TMP)4] 2 but shows quite different luminescence in response to the external stimuli. Especially, during the mechanical grinding, the relative intensities of HE and LE of 1 varied with a concomitant hypsochromic shift, and when the temperature was decreased from 300 to 5 K, unprecedented contrary thermo-responsive trend for single crystal and powered samples (blueshift of single crystals and redshift of powdered samples) was observed. These distinct characters of 1 should be due to the different molecular packing modes, metallic interactions and the unique character of Ag(I) ion.
Highlights
Similar to the Cu(I) ions of the stimuli-responsive copper(I) halide clusters, Ag(I) ions possess the tetrahedral coordination geometry and exhibit metallophilic interactions; emissive silver(I) halide compounds are potential stimuli-sensitive materials
An unprecedented contrary thermo-responsive trend was observed for single crystal and powder samples
X-ray diffraction data reveals that compound 1 contains cubane [Ag4I4] clusters with four silver ions and four iodide ions alternatively occupying the corners of a distorted cube
Summary
Similar to the Cu(I) ions of the stimuli-responsive copper(I) halide clusters, Ag(I) ions possess the tetrahedral coordination geometry and exhibit metallophilic interactions; emissive silver(I) halide compounds are potential stimuli-sensitive materials. (1) Ag(I) ion is more inert to oxidation than Cu(I), often resulting in an absence of the low-energy MLCT state and reduced complexity of the origin of stimuli-responsive luminescence[15]; (2) In contrast to Cu(I) complexes, the geometrical arrangements and local environment around Ag(I) ions drastically affect luminescence[16]. Considering these similarities and differences, scholars have focused on stimuli-responsive luminescence of emissive silver(I)-halide materials[17]. These results contribute to understanding the effects of the metallophilic interactions, molecular structure, and packing mode for stimuli-responsive luminescence
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