A New 3,5-Bisporphyrinylpyridine Derivative as a Fluorescent Ratiometric Probe for Zinc Ions


A new 3,5-disubstituted pyridine with two porphyrin moieties was prepared through an efficient synthetic approach involving 2-formyl-5,10,15,20-tetraphenylporphyrin (1), piperidine, and catalytic amounts of [La(OTf)(3)]. 3,5-Bis(5,10,15,20-tetraphenylporphyrin-2-ylmethyl)pyridine (2) was fully characterized and its sensing ability towards Zn2+, Cu2+, Hg2+, Cd2+, and Ag+ was evaluated in solution by absorption and fluorescence spectroscopy and in gas phase by using matrix-assisted laser desorption/ionization (MALDI)-TOF mass spectrometry. Strong changes in the ground and excited state were detected in the case of the soft metal ions Zn2+, Cd2+, Hg2+, and Cu2+. A three-metal-per-ligand molar ratio was obtained in all cases and a significant ratiometric behavior was observed in the presence of Zn2+ with the appearance of a new band at 608nm, which can be assigned to a metal-to-ligand charge transfer. The system was able to quantify 79ppb of Zn2+ and the theoretical calculations are in accordance with the stoichiometry observed in solution. The gas-phase sensorial ability of compound 2 towards all metal ions was confirmed by using MALDI-TOF MS and in solid state by using polymeric films of polymethylmethacrylate (PMMA) doped with ligand 2. The results showed that compound 2 can be analytically used to develop new colorimetric molecular devices that are able to discriminate between Hg2+ and Zn2+ in solid phase. The crystal structure of Zn-II complex of 3,5-bisporphyrinylpyridine was unequivocally elucidated by using single-crystal X-ray diffraction studies.






Moura, NMM; Nunez, C; Santos, SM; Faustino, MAF; Cavaleiro, JAS; Paz, FAA; Neves, MGPMS; Capelo, JL; Lodeiro, C

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Authors are grateful to the Universidade de Aveiro, Fundacao para a Ciencia e a Tecnologia (FCT), European Union, QREN, FEDER and COMPETE for funding the QOPNA research unit (project PEst-C/QUI/UI0062/2013, FCOMP-01-0124-FEDER-037296). We acknowledge the Portuguese National NMR Network (RNRMN), supported by funds from FCT, Scientific PRO-TEOMASS Association (Portugal), CICECO (PEst-C/CTM/LA0011/2013, FCOMP-01-0124-FEDER-037271) and REQUIMTE (PEst-C/EQB/La0006/2013) for general funding and Fundacao para a Ciencia e a Tecnologia (FCT) for specific funding towards the purchase of the single-crystal X-ray diffractometer. N.M.M.M. and S. M. S. thank FCT/MEC for their Postdoctoral grant SFRH/BPD/84216/2012 and SFRH/BPD/64752/2009. C.N. thanks the Xunta de Galicia (Spain) for her postdoctoral contract (I2C program). We thank M. Graca O. Santana-Marques for the helpful comments and discussion on MALDI-TOF MS studies.

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