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Title: Synthesis and structural, photophysical, electrochemical redox and axial ligation properties of highly electron deficient perchlorometalloporphyrins and selective CN- sensing by Co(ii) complexes
Authors: Chaudhri N.
Butcher R.J.
Sankar, Muniappan
Published in: New Journal of Chemistry
Abstract: A straightforward synthetic route has been adopted to synthesize highly nonplanar electron deficient perchlorometallo-porphyrins. Herein, we report the synthesis and characterization of MTPP(NO2)Cl7 where M = CoII, NiII, CuII and ZnII. Further, we examined their optical and electrochemical redox properties and the results are compared with MTPPCl8. MTPP(NO2)Cl7 exhibited red-shifted (∼10-15 nm) absorption spectra relative to MTPPCl8 due to the strong electron withdrawing nature of the nitro group. Mixed β-substitution alters the electrochemical redox properties to such an extent that an appreciable increase in the anodic shift in reduction potential (200-300 mV) is observed for MTPP(NO2)Cl7 relative to MTPPCl8 whereas only a minimal shift (15-50 mV) in the oxidation potential is observed. Nonplanarity of the macrocyclic core was investigated by single crystal X-ray analysis and DFT calculations. A higher ΔCβ (0.706 Ã…) for 1d as compared to 2d (0.642 Ã…) undoubtedly signifies nonplanarity induced by the nitro group. To substantiate the effect of mixed substitution, we performed axial ligation studies of Zn(ii) complexes with nitrogenous bases and basic anions and found higher log:β2 values as well as a linear relation between log:β2 and pKa as compared to perbromoporphyrins. Highly electron deficient β-substituted Co(ii) porphyrins (1a and 2a) were utilized as novel sensors for selective rapid visual detection of CN- ions. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
Citation: New Journal of Chemistry (2018), 42(10): 8190-8199
Issue Date: 2018
Publisher: Royal Society of Chemistry
ISSN: 11440546
Author Scopus IDs: 56450499000
Author Affiliations: Chaudhri, N., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Butcher, R.J., Department of Chemistry, Howard University, Washington, DC 20059, United States
Sankar, M., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
Funding Details: We are grateful for the financial support provided by the Engineering Research Board (EMR/2016/004016). NC thanks the Council of Scientific and Industrial Research (CSIR), India for the SRF fellowship.
Corresponding Author: Sankar, M.; Department of Chemistry, Indian Institute of Technology RoorkeeIndia; email:
Appears in Collections:Journal Publications [CY]

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