Antenna effect on Zn(II) porphyrin–based molecular ensembles for the detection of 2,4-dinitrophenol through energy and electron transfer process

Two modular systems were synthesized composed of triphenylamine (ZnTPAP) and pyrene (ZnPyP) covalently linked at meso position of the Zn(II) porphyrins. Both compounds behaved as energy transfer antenna and orthogonal units to enhance the electron donating ability of Zn(II) porphyrins. Detailed photophysical and aggregation studies reveal that an appreciable electronic interaction exists between peripheral units to the porphyrin π-system so that they behave like strong donor materials. The electrochemical and computational studies demonstrate delocalization of the frontier highest occupied molecular orbital (−5.08 eV) over the triphenylamine entities (ZnTPAP) in addition to the porphyrin macrocycle. Fluorescence experiments with ZnTPAP and ZnPyP in the presence of different nitro analytes at various concentrations show turn-off fluorescence behaviour and exhibit superior selectivity towards 2,4-dinitrophenol (DNP) with limit of detection (LOD) of ~ 2.3 and 9.2 ppm for ZnTPAP and ZnPyP. Photoinduced electron transfer process is involved in the static and dynamic fluorescence quenching process. A Stern–Volmer quenching association constant (K_sv) determination revealed that ZnTPAP is more sensitive than the ZnPyP. This is attributed to the strong donating behaviour of TPA units caused by intermolecular interaction through metal center and strong π–π interactions with nitro analytes. The present study provides new insights into the ability to tune the affinity and selectivity of porphyrin-based sensors utilising electronic factors associated with the central Zn(II) ion. Furthermore, a smartphone-interfaced portable fluorimetric method by recognising colour variations in RGB and the luminance (L) values facilitate sensitive and real-time sensing at low concentration levels will have a significant impact on development of a new class of chemosensors.

Graphical Abstract