Anion and cation triggered modulation of optical properties of a pyridyl-imidazole receptor rigidly linked to pyrene and construction of INHIBIT, OR and XOR molecular logic gates: A combined experimental and DFT/TD-DFT investigation

• Published in: Sensors and actuators. B, Chemical Chemical, 2015-01, Vol.206, p.701-713
• Main Authors: Mardanya, Sourav, Karmakar, Srikanta, Das, Shyamal, Baitalik, Sujoy
• Format: Article
• Language: English
• Subjects: DFT/TD-DFT; Fluoride; Molecular logic gates; Pyrene; Pyridyl-imidazole; Zinc
• ISSN: 0925-4005; 1873-3077
• DOI: 10.1016/j.snb.2014.09.043

Based on the response profiles in terms of absorption and emission intensity and wavelength toward ionic inputs we developed a pyridyl-imidazole-based receptor which can mimic the functions of INHIBIT, OR and XOR logic gates. •A pyridyl-imidazole based bifunctional receptor rigidly linked to pyrene has been synthesized and structurally characterized.•The optical properties of the receptor were significantly modulated by selective anions and cations.•Based on the response profiles in terms of the optical response toward ionic inputs INHIBIT, OR and XOR molecular logic gates have been constructed.•DFT and TD-DFT calculations were performed in order to gain deeper insight into the geometric and electronic properties of the compounds. A pyridyl-imidazole based bifunctional receptor 10-pyridin-2-yl-9H-9,11-diaza-cyclopenta[e]pyrene (HImzPPy), wherein a pyridyl-imidazole moiety linked to 1,6-position of pyrene, has been synthesized and characterized by standard analytical and spectroscopic techniques. Unambiguous structure of the compound in the solid state was determined by single crystal X-ray crystallography. The compound was crystallized in orthorhombic system with P 21 21 21 space group. The absorption and emission properties of the receptor were modulated by selective anions and transition metal cations. Based on the response profiles in terms of absorption and emission intensity and wavelength toward Zn2+ and F− or Cd2+ and F− ions, we developed a molecular system capable of mimicking the functions of INHIBIT, OR and XOR logic gates. We have also optimized the geometries of the receptor and it is imidazole NH deprotonated form (ImzPPy) and the Zn2+ complex of HImzPPy (Zn(HImzPPy)2]2+) in both ground and excited states. We then proceed to compute the absorption and emission spectral behaviors of the compounds in solution using a TD-DFT approach to understand the nature of the underlying excited states involved in the transition processes. The experimentally observed shifts in the absorption and emission bands of the receptor due to the interaction with selective anions and cations are also reproduced by our calculations.