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.
ABSTRACT
A chiral C3-symmetric cubane cluster, [Cu4I4(TMP)4], with enough long Cu-Cu distances to eliminate the presence of Cu-Cu interaction has been synthesized and characterized, which shows simultaneous luminescent thermochromism, solvatochromism, vapochromism, and mechanochromism and is a multiply stimuli-responsive chromic luminescent material. This complex could partly transform into a yellow-emissive bicapped cubane cluster, [Cu6I6(TMP)4(MeCN)2], in acetonitrile (MeCN) vapor and solution, which provides some insight into vapochromism and solvatiochromism. This work challenges and makes us reconsider the conventional viewpoint that Cu-Cu interaction is involved in thermochromism and mechanochromism of copper complexes.