Dicyanamide-intertwined assembly of two new Zn complexes based on N2O4-type pro-ligand: Synthesis, crystal networks, spectroscopic insights, and selective nitroaromatic turn-off fluorescence sensing

Abstract

Two new dicyanamide bridged multinuclear Zn complexes, [Zn2(L1)(µ1,5-dca)2(µ1-dca)]n (1) and [Zn2(L2)(µ1,5-dca)2(µ1-dca)]n (2) have been synthesized using N2O4-based pro-ligands (H2L1 = N,N′-bis(5-bromo-3-methoxysalicylidenimino)-1,3-diaminopropane, H2L2 = N,N′-bis(3-ethoxysalicylidene)-2,2-dimethyl-1,3-propanediamine) and characterized by microanalytical and spectroscopic techniques. Both complexes are stable in solution and solid-state. Thermogravimetric analysis (TGA) findings showed that complexes are stable at room temperature. Single-crystal X-ray diffraction (SCXRD) has proven that complexes are identical structures where two zinc metal ions are crystallographically independent. The directional properties of dicyanamide co-ligands via µ1,5 bridging have resulted in different connectivity of zinc metal ions leading to 1D templates. SCXRD revealed some notable non-covalent interactions (π⋯π, C-H····π, and H-bonding) in their solid-state crystal structures. 1–2 have strong fluorescence behaviour over pro-ligands, which may be quenched in the presence of various electron-deficient explosive nitroaromatic compounds (epNACs). Complex 2 fluorescence intensity is sharper than 1; hence the former retained high sensitivity and selectivity for trinitrophenol (TNP). The enhancement of fluorescence mechanism, detection limit (LOD), and the quenching constant (KSV) have been calculated using the Stern-Volmer equation (SV), where the KSV value for TNP is found to be 1.542 × 104 M−1. The solution phase quenching mechanism has been rationalized by (a) electrostatic interactions through charge-transfer complex, (b) photo-induced electron transfer (PET) by the HOMO-LUMO energy gap via DFT, and (c) fluorescence resonance energy transfer (FRET). Finally, complex 2 is applied as a sensor by turn-off fluorescence response to detecting TNP nitroaromatics in the DMF medium.