Aza-phenol Based Macrocyclic Probes Design for “CHEF-on” Multi Analytes Sensor: Crystal Structure Elucidation and Application in Biological Cell Imaging

[Image: see text] Metal bound macrocyclic compounds found in biological systems inspired us to design and synthesize two Robson-type macrocyclic Schiff-base chemosensors, H(2)L1 (H(2)L1=1,11-dimethyl-6,16-dithia-3,9,13,19-tetraaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1,11-diol) and H(2)L2 (H(2)L2=1,11-dimethyl-6,16-dioxa-3,9,13,19-tetraaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1,11-diol). Both the chemosensors have been characterized with different spectroscopic techniques. They act as multianalyte sensor and exhibit “turn-on” fluorescence toward different metal ions in 1X PBS (Phosphate Buffered Saline) solution. In presence of Zn(2+), Al(3+), Cr(3+) and Fe(3+) ions, H(2)L1 exhibits ∼6-fold enhancement of emission intensity, while H(2)L2 shows ∼6-fold enhancement of emission intensity in the presence of Zn(2+), Al(3+) and Cr(3+) ions. The interaction between the different metal ion and chemosensor have been examined by absorption, emission, and (1)H NMR spectroscopy as well as by ESI-MS(+) analysis. We have successfully isolated and solved the crystal structure of the complex [Zn(H(2)L1)(NO(3))]NO(3) (1) by X-ray crystallography. The crystal structure of 1 shows 1:1 metal:ligand stoichiometry and helps to understand the observed PET-Off-CHEF-On sensing mechanism. LOD values of H(2)L1 and H(2)L2 toward metal ions are found to be ∼10(–8) and ∼10(–7) M, respectively. Large Stokes shifts of the probes against analytes (∼100 nm) make them a suitable candidate for biological cell imaging studies. Robson type phenol based macrocyclic fluorescence sensors are very scarce in the literature. Therefore, the tuning of structural parameters as the number and nature of donor atoms, their relative locations and presence of rigid aromatic groups can lead to the design of new chemosensors, which can accommodate different charged/neutral guest(s) inside its cavity. The study of the spectroscopic properties of this type of macrocyclic ligands and their complexes might open a new avenue of chemosensors.