Abstract
Unsymmetrical meso-functionalized ‘push-pull’ porphyrinoid derivatives have been widely used in the areas of solar cells, photocatalysis, toxic ion sensing and nonlinear optics (NLO).1 They have been widely explored due to their ease of synthesis and facile functionalization whereas limited reports on β-substituted ‘push-pull’ π-extended porphyrinoids due to lack of synthetic methodologies. However, it is found that the latter ones exhibit unique physicochemical and electrochemical redox properties with interesting material and medicinal applications.Recently, our group has reported the facile synthesis of β-functionalized, β-meso-o-phenyl and β-β’ fused corroles, chlorins, and porphyrins with mixed substitutents pattern.2,3 The crystal structure analyses of highly substituted corroles, porphyrins and chlorins revealed quasiplanar to nonplanar saddle shape conformation. Notably, nonplanarity of the porphyrinoid core was controlled and modified by varying in size, shape, number and the electronic nature of β-substituents. These porphyrinoids exhibited highly red-shifted electronic spectra upto NIR region with dramatic decrement in HOMO-LUMO gap. In addition, the redox tunability was achieved by introducing both electron donating and withdrawing β-substituents into the tetrapyrrole skeleton which led to nonplanarity with enormous ‘cross polarization’ which has great potentiality to use in nonlinear optics (NLO). In this presentation, the facile synthesis, spectral and intriguing redox properties of these porphyrins and their potential application in materials chemistry will be discussed in detail. REFERENCES: (a) Urbani, M.; Grätzel, M. ; Nazeeruddin, M. K.; Torres, T. Chem. Rev., 2014, 114, 12330-12396. (b) Hiroto, S.; Miyake, Y.; Shinokubo, H. Chem. Rev., 2017, 117, 2910-3043.(a) Kumar, R.; Sankar, M. Inorg. Chem., 2014, 53, 12706-12719. (b) Yadav, P.; Sankar, M. Dalton Trans., 2014, 43, 14680-14688. (c) Kumar, R.; Chaudhri, N.; Sankar, M. Dalton Trans., 2015, 44, 9147-9157. (d) Kumar, R.; Chaudhary, N.; Sankar, M.; Maurya, M. R. Dalton Trans., 2015, 44, 17720-17729. (e) Grover, N.; Sankar, M.; Song Y.; Kadish, K. M. Inorg. Chem., 2016, 55, 584-597. (f) Chahal, M. K.; Sankar, M. Dalton Trans., 2016, 45, 16404-16412. (g) Sankar, M. et al. Inorg. Chem., 2017, 56, 8527-8537.(a) Chaudhri, N.; Grover, N.; Sankar, M. Inorg. Chem., 2017, 56, 424-437. (b) Chaudhri, N.; Grover, N.; Sankar, M. Inorg. Chem., 2017, 56, 11532-11545. (c) Sankar, M. et al, J. Mater. A, 201 7, 5, 6263-6276. (d) Sankar, M. et al, ACS Appl. Energy Mater., 2018, 1, 2793-2801. (e) Sankar, M. et al. Inorg. Chem., 2018, 57, 1490-1503. (f) Chaudhri, N.; Grover, N.; Sankar, M. Inorg. Chem., 2018, 57, 6658-6668. (g) Chaudhri, N.; Grover, N.; Sankar, M. Inorg. Chem., 2018, 57, 11349-11360. (h) Sankar, M. et al. Inorg. Chem., 2018, 57, 13213-13224. (i) Grover, N.; Chaudhri, N.; Sankar, M. Inorg. Chem., 2019, 58, 2514-2522. (j) Dar, T. A.; Uprety, B.; Sankar, M.; Maurya, M. R. Green Chem., 2019, 21, 1757-1768. (k) Rathi, P.; Butcher, R.; Sankar, M. Dalton Trans., 2019, 48, 15002-15011. (l) Chahal, M. K. et al. Inorg. Chem., 2019, 58, 14361-14376. (m) Chaudhri, N. et al. Inorg. Chem., 2020, 59, 1481-1495. (n) Grover, N and Sankar, M. Chem. Asian J. 2020, 15, 2192-2197.
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