Mechanochromic Luminescence Switch of Platinum(II) Complexes with 5-Trimethylsilylethynyl-2,2′-bipyridine

Abstract

Planar platinum(II) complexes Pt(bpyC≡CSiMe(3))(C≡CC(6)H(4)R-4)(2) (R = H (1), Bu(t) (2)) with 5-trimethylsilylethynyl-22'-bipyridine show an unusual, reversible, and reproducible mechanical stimuli-responsive color and luminescence switch. When crystalline 1 or 2 is ground, bright yellow-green emitting is immediately converted to red luminescence with an emission red shift of 121-155 nm for 1 or 53-89 nm for 2. Meanwhile, the crystalline state is transformed to an amorphous phase that can be reverted to the original crystalline state by organic vapor adsorbing or heating, along with red luminescence turning back to yellow-green emitting. The reversibility and reproducibility of luminescence mechanochromic properties have been dynamically monitored by the variations in emission spectra and X-ray diffraction patterns. The drastic grinding-triggered emission red shift is likely involved in the formation of a dimer or an aggregate through Pt-Pt interaction, resulting in a conversion of the (3)MLCT/(3)LLCT emissive state in the crystalline state into the (3)MMLCT triplet state in the amorphous phase. Compared with the drastic grinding-triggered emission red shift in 1 (121-155 nm), the corresponding response shift in 2 (53-89 nm) is much smaller since a bulky tert-butyl in C≡CC(6)H(4)bu(t)-4 induces the planar platinum(II) molecules to stack through a longer Pt-Pt distance and less intermetallic contact compared with that in 1, as suggested from EXAFS studies.