Copper(II) Ion Promoted Reverse Solvatochromic Response of the Silatrane Probe to Spectral Shifts: Preferential Solvation and Computational Approach.

The unique solvatochromic attitude of an analyte owing to its coordination with metal ions in solvents of different polarities is challenging. Herein, we introduce two new solvatochromic 4-(pentan-3-yl) benzaldehyde-based triazolyl silatrane probes (5 and 6). The solvatochromic behavior of both probes 5 and 6 was studied using Reichardt's E (30) and the Kamlet-Taft empirical scale by UV-visible spectra in 14 solvents (hydrogen-bond donor (HBD) and non-HBD), and the results show that probes 5 and 6 exhibit reverse solvatochromism. Probe 5 witnessed an enhancement in this behavior upon coordination with the Cu2+ ion in MeCN/MeOH solvents due to the intramolecular charge transfer (ICT) process. Interestingly, the binding of probe 5 with Cu2+ ions resulted in an instant color change in MeCN and MeOH from pale yellow to light blue and brown-red, respectively, which can be easily detected by the "naked eye". A solvatochromic study of the complex 5-Cu2+ in binary mixtures of polar aprotic and polar protic solvents (MeCN/MeOH) discloses that the latter are more preferred over polar aprotic solvents in the solvation microsphere. The entire metal coordination process of probe 5 toward the Cu2+ ion can be visualized and was further evaluated by UV-vis/fluorescence spectral titrations, Fourier transform infrared (FT-IR) spectroscopy, and theoretical calculations employing density functional theory (DFT) and time-dependent-DFT (TD-DFT). The proposed analytical approach is believed to play a crucial role in the solvatochromic study of higher coordinated silicon compounds, which may be utilized to develop a solvent-dependent sensor.

Molecular keypad controlled circuit for Ce(iii) and NO3 - ions recognition by µw synthesized silicon-embedded organic luminescent sensor.

This report demonstrates the mimicking of an electronic circuit diagram towards Ce(iii) ion sensing response supported by molecular keypads. The probe naphthyl based triazole linked silatrane (NTS) was efficiently synthesized using a series of microwave mediated reactions. The luminescent sensor NTS was explored for the ion sensing response towards Ce(iii) ions using DMSO and DMSO : H2O 4 : 1 (v/v) as solvent media, respectively. The role of water in Ce(iii) ion sensing was detected as 'turn-off' response that contradicts the 'turn-on' with DMSO. Further, the sensing of NO3 - ions by NTS-Ce(iii) ensemble was associated with blue shift on absorption maxima. These mimicking response studies were sketched as circuit diagrams assisted by molecular keypad behaviour as IMPLICATION output logic gate.