Details

Autor(en) / Beteiligte

• Chahal, Mandeep K
• Sankar, Muniappan
• Butcher, Ray J

Titel

An insight into the communication between β-olefin/phenyl olefin-mediated acceptors and porphyrin π-system: a way to establish porphyrin based chemodosimeters and chemosensors

Ist Teil von

• Physical chemistry chemical physics : PCCP, 2017-02, Vol.19 (6), p.4530-4540

Ort / Verlag

England

Erscheinungsjahr

2017

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The synthesis of three new classes of mixed β-pyrrole substituted tetraphenylporphyrins, MTPP(R), MTPP(Br) (R) (where R = -CH[double bond, length as m-dash]C(CN) , -CH[double bond, length as m-dash]C(CN)(COOC H ), -CH[double bond, length as m-dash](CN)(COOH) and M = 2H, Ni(ii), Cu(ii)) and MTPP(NO )(Ph-p-R') (R' = -CHO and -CH[double bond, length as m-dash]C(CN) and M = 2H, Ni(ii), Cu(ii)) have been reported. The crystal structures of CuTPP(Br) -ECA (7a), NiTPP(NO )(Ph-p-CHO) (9) and NiTPP(NO )(Ph-p-CH[double bond, length as m-dash](CN) ) (10) are highly nonplanar among β-trisubstituted porphyrins reported to date as evidenced from the mean displacement of β-pyrrole carbon (ΔC ) in the range ±(0.39-0.674) Å. The olefin mediated ethyl cyanoacetate is in plane with the porphyrin core in CuTPP(Br) -ECA (the dihedral angle relative to the pyrrole NC -mean plane is 39.81°) while dicyanovinyl stays aside for NiTPP(NO )(Ph-p-CH[double bond, length as m-dash](CN) ) (dihedral angles relative to the pyrrole NC -mean plane are 75.03° and 67.47°). NiTPP-MN (2), NiTPP-ECA (3), NiTPP(Br) -MN (6) and NiTPP(Br) -ECA (7) act as chemodosimeters for toxic CN ions whereas NiTPP-CAA (4) and NiTPP(Br) -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(NO )(Ph-p-CH[double bond, length as m-dash](CN) ) (10) also acts as chemodosimeter for CN ions but no vivid changes are observed via different spectroscopic methods.