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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/3576
Title: An insight into the communication between β-olefin/phenyl olefin-mediated acceptors and porphyrin Ï€-system: A way to establish porphyrin based chemodosimeters and chemosensors
Authors: Chahal M.K.
Sankar M.
Butcher R.J.
Published in: Physical Chemistry Chemical Physics
Abstract: The synthesis of three new classes of mixed β-pyrrole substituted tetraphenylporphyrins, MTPP(R), MTPP(Br)2(R) (where R = -CHC(CN)2, -CHC(CN)(COOC2H5), -CH(CN)(COOH) and M = 2H, Ni(ii), Cu(ii)) and MTPP(NO2)(Ph-p-R′)2 (R′ = -CHO and -CHC(CN)2 and M = 2H, Ni(ii), Cu(ii)) have been reported. The crystal structures of CuTPP(Br)2-ECA (7a), NiTPP(NO2)(Ph-p-CHO)2 (9) and NiTPP(NO2)(Ph-p-CH(CN)2)2 (10) are highly nonplanar among β-trisubstituted porphyrins reported to date as evidenced from the mean displacement of β-pyrrole carbon (ΔCβ) in the range ±(0.39-0.674) Ã…. The olefin mediated ethyl cyanoacetate is in plane with the porphyrin core in CuTPP(Br)2-ECA (the dihedral angle relative to the pyrrole NC4-mean plane is 39.81°) while dicyanovinyl stays aside for NiTPP(NO2)(Ph-p-CH(CN)2)2 (dihedral angles relative to the pyrrole NC4-mean plane are 75.03° and 67.47°). NiTPP-MN (2), NiTPP-ECA (3), NiTPP(Br)2-MN (6) and NiTPP(Br)2-ECA (7) act as chemodosimeters for toxic CN- ions whereas NiTPP-CAA (4) and NiTPP(Br)2-CAA (8) act as chemosensors to detect toxic ions such as CN-, F- and OAc- depending on the acceptor strength and an obstacle in the conjugation pathway. The dicyanovinyl group in the phenyl olefinic-mediated porphyrin NiTPP(NO2)(Ph-p-CH(CN)2)2 (10) also acts as chemodosimeter for CN- ions but no vivid changes are observed via different spectroscopic methods. © the Owner Societies 2017.
Citation: Physical Chemistry Chemical Physics (2017), 19(6): 4530-4540
URI: https://doi.org/10.1039/c6cp08396j
http://repository.iitr.ac.in/handle/123456789/3576
Issue Date: 2017
Publisher: Royal Society of Chemistry
ISSN: 14639076
Author Scopus IDs: 55696261900
6701530390
7201947292
Author Affiliations: Chahal, M.K., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Sankar, M., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Butcher, R.J., Department of Chemistry, Howard University, Washington, DC 20059, United States
Funding Details: We sincerely thank the Science and Engineering Research Board (SB/FT/CS-015/2012), the Board of Research in Nuclear Science (2012/37C/61/BRNS) and the Council of Scientific and Industrial Research (01(2694)/12/EMR-II) for financial support. MKC thanks the University Grants Commission (UGC), India for senior research fellowship.
Corresponding Author: Sankar, M.; Department of Chemistry, Indian Institute of Technology RoorkeeIndia; email: sankafcy@iitr.ac.in
Appears in Collections:Journal Publications [CY]

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