Precise molecular design for a twisted pyrene-thiophene based mechanofluorochromic probe with large Stokes shift and feasibility study towards security ink and re-writable papers

Abstract

The creation of MFC-active smart molecules by tuning functionality has received considerable attention owing to its versatile applicability. Pyrene-based twisted donor–acceptor (D–A) dyes (PySS and PySP) have been synthesized and characterized. Here, the pyrene is directly connected with thiophene, and this unit is further linked terminally to photoactive species (thiophene/pyridine) via a four-carbon unit conjugated spacer. These molecules show excellent solvatochromic properties, with a substantial shifting of the emission wavelength (PySS- 147 nm and PySP- 130 nm). The lowest transition state contains a significant contribution from ICT characteristics, as evidenced by spectral analysis and computational calculations. Moreover, these are identified as ‘aggregation-induced enhanced emission’ (AIEE) active compounds and exhibit mechanofluorochromism (MFC). By grinding, PySS and PySP display MFC features with 50 nm and 54 nm red shifting, respectively. Interestingly, PySS shows a gradual emission change from green (510 nm) to orange emission (578 nm) by gradually changing the pressure with a hydraulic press (0 to 12.5 tons). The single crystal structure of both compounds was investigated to understand the structure–property relationship for MFC. The crystal packing shows that the twisted molecules (dihedral angle between pyrene and thiophene is 59.36° and 56.93° for PySS and PySP, respectively) are loosely bound with several weak interactions (C–H⋯π, C–π⋯H, H⋯H, C–H⋯O). Interestingly, it was observed that two molecules in a unit cell are arranged in an antiparallel fashion; these molecular pairs are linearly connected to another pair axially, forming a long one-dimensional chain-type arrangement. On applying pressure, these twisted molecular pairs may slowly planarize, leading the molecules to come closer, thus changing the molecular interaction and the emission properties. A feasibility study of the potentiality of using these compounds in data encryption–decryption and security ink has also been demonstrated.