Low-cost photo-switches based on stilbene-appended Zn(II)-terpyridine complexes

Abstract

We report herein the synthesis, characterization, photophysics, and photo-isomerization behaviors of three Zn(II)-terpyridine complexes of the type [Zn(tpy-pvp-X)₂]²⁺ (X = H, Me, and NO₂) covalently tethered with stilbene moiety. The complexes exhibit absorption bands stretching up to the edge of the visible domain due to ligand → ligand charge transfer (LLCT) transitions and strong emission at room temperature in the visible due to radiative deactivation of ³LLCT state having lifetime within 1.0-3.0 ns. The stilbene motifs in the complexes undergo trans to cis isomerization upon irradiating with UV and visible light accompanied by significant alteration of their absorption, emission, and ¹H NMR spectral profiles. Apart from the variation of electron donating and electron withdrawing substituent (X), the isomerization studies were also carried out in three different solvents (DCM, MeCN, and DMSO) to further tune their kinetic and thermodynamic parameters. The rate, rate constant and quantum yield of isomerization were estimated in all the solvents. The reverse process (cis to trans) also occurs very slowly on keeping but could be accelerated upon heating. Trans to cis photoisomerization leads to quenching of emission in case of 1 and 2, whereas backward thermal cis to trans conversion leads to restoration of emission. By contrast, for the nitro-derivative (3) forward process induces emission enhancement, while backward process gives rise to emission quenching. In essence, "on-off" and "off-on" emission switching is feasible for 1 and 2, whereas "off-on" and "on-off" emission switching occurs in case of 3. Emission spectral responses upon successive action of photonic and thermal input lead to the fabrication of INHIBIT and IMPLICATION logic gates. DFT and TD-DFT computational investigations were also undertaken to visualize their electronic structures, correct assignment of the spectral bands, and mode of isomerization process.

Keywords: DFT–TDDFT; Logic gate; Photo-switching; Trans–cis photoisomerisation; Zn(II)–terpyridine complexes.