TY - JOUR
T1 - A new 3,5-bisporphyrinylpyridine derivative as a fluorescent ratiometric probe for zinc ions
AU - Moura, Nuno M. M.
AU - Núñez, Cristina
AU - Santos, Sérgio M.
AU - Faustino, M. Amparo F.
AU - Cavaleiro, José A. S.
AU - Almeida Paz, Filipe A.
AU - Neves, M. Graça P M S
AU - Capelo, José Luis
AU - Lodeiro, Carlos
N1 - 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.
PY - 2014/5/26
Y1 - 2014/5/26
N2 - 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 Zn(2+), Cu(2+), Hg(2+), Cd(2+), 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 Zn(2+), Cd(2+), Hg(2+), and Cu(2+). A three-metal-per-ligand molar ratio was obtained in all cases and a significant ratiometric behavior was observed in the presence of Zn(2+) with the appearance of a new band at 608 nm, which can be assigned to a metal-to-ligand charge transfer. The system was able to quantify 79 ppb of Zn(2+) 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 Hg(2+) and Zn(2+) 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.
AB - 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 Zn(2+), Cu(2+), Hg(2+), Cd(2+), 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 Zn(2+), Cd(2+), Hg(2+), and Cu(2+). A three-metal-per-ligand molar ratio was obtained in all cases and a significant ratiometric behavior was observed in the presence of Zn(2+) with the appearance of a new band at 608 nm, which can be assigned to a metal-to-ligand charge transfer. The system was able to quantify 79 ppb of Zn(2+) 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 Hg(2+) and Zn(2+) 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.
KW - fluorescent probes
KW - porphyrinoids
KW - sensors
KW - X-ray diffraction
KW - zinc
UR - http://www.scopus.com/inward/record.url?scp=84929048011&partnerID=8YFLogxK
U2 - 10.1002/chem.201402270
DO - 10.1002/chem.201402270
M3 - Article
C2 - 24782336
SN - 1521-3765
VL - 20
SP - 6684
EP - 6692
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 22
ER -