Chlorodiphenyltin(IV) dithiocarbamate complexes as chemodosimeters and host for anions and neutral compounds in solution

The chlorodiphenyltin(IV) dithiocarbamate complexes 1–5 with general formula {(Ph2SnCl)dtc} (dtc = R1R2NCS2−; 1, R1 = Bn, R2 = 9-anthrylmethyl; 2, R1 = Bn, R2 = 9-phenanthrylmethyl; 3, R1 = Bn, R2 = 1-pyrenylmethyl; 4, R1 = 1-naphthylmethyl, R2 = 1-pyrenylmethyl; 5, R1 = R2 1-pyrenylmethyl) have been tested as host for anions and neutral amines in acetonitrile by spectrophotometric UV/Vis titrations. In addition, the titrations of the complexes 1 and 5 were studied in chloroform by 1H and 119Sn NMR spectroscopy. It was found that anions as acetate, benzoate, and dihydrogen phosphate cause a displacement of the dithiocarbamate ligands of metallic center independently of the aromatic nature of the substituents on the nitrogen atom functioning as chemodosimeters in which the indicator is displaced. However, some aliphatic amines and aromatic methylene amines and its aromatic analogs can act as guests with binding constants in the range of 103 to 106 M−1. Also, in these cases compound 5 functions as chemodosimeter without displacement of the indicator. According to 1H, 13C, 119Sn NMR data and using DFT (B3LYP) and Poisson–Boltzmann (PB) to model the solvent, structures of the complexes are proposed in which the hydrophobic and π–π interactions are suggested as the dominant interactions.

Graphical abstractPolycyclic aromatic dithiocarbamate-tin(IV) complexes were studied as potential host of anions and neutral aromatic compounds and were found that dithiocarbamates can function as a chemodosimeters with binding constants in acetonitrile in the range of 103 to 106 M−1 for the neutral amines and aromatic compounds.Figure optionsDownload full-size imageDownload as PowerPoint slide