ABSTRACT
This study focuses on the synthesis, characterization, and fluorometric sensing of 2,3-diphenylethynyl-meso-tetraphenylporphyrin (H₂TPP(PE)₂) and its zinc (II) metal derivatives. The synthesized compounds were obtained through a series of chemical transformations starting from meso-tetraphenylporphyrin, which included bromination, reduction, palladium-catalysed coupling and metalation with Zn (II). The resulting porphyrins were characterized using UV-Visible spectroscopy, proton nuclear magnetic resonance (¹H NMR), high-resolution mass spectrometry (HRMS), and other techniques to confirm their structures. The UV-Vis absorption spectra revealed a bathochromic shift in the Soret and Q bands with increasing substitution, particularly for the H₂TPP(PE)₂ and its Zn (II) derivative, indicating the influence of electron-withdrawing substituents. Furthermore, these porphyrins demonstrated promising fluorometric sensing properties, particularly in the detection of cyanide (CN⁻) ions, exhibiting significant spectral changes upon interaction. This study underscores the potential of these modified porphyrins as effective materials for environmental pollutant detection and highlights their utility in optoelectronic and sensor applications. The findings pave the way for further development of these compounds as candidate materials for advanced environmental monitoring and other technological applications.
AUTHOR AFFILIATIONS
Department of Zoology and Environmental Sciences, Punjabi University Patiala, Punjab, India
CITATION
Walia GK, Parmar M and Chopra D (2025) Synthesis, Characterization and Fluromatic Sensing of 2, 3-diphenylethynyl-meso-tetraphenylporphyrin (H2TPP(PE)2) and its Zn (II)-Metal Derivatives. Environmental Science Archives 4(2): 765-773.
REFERENCES
Adler AD, Longo FR, and Shergalis W (1964) Mechanistic investigations of porphyrin syntheses. I. Preliminary studies on ms-tetraphenylporphin. Journal of the American Chemical Society, 86(15): 3145-3149.
Adler AD, Longo FR, Finarelli JD, et al. (1967) J. Assouri L. Korsakoff. Journal Organic Chemistry, 32: 476-476.
Casademont‐Reig I, Guerrero‐Avilés R, Ramos‐Cordoba E, et al. (2021) How Aromatic Are Molecular Nanorings? The Case of a Six‐Porphyrin Nanoring. Angewandte Chemie, 133(45): 24282-24290.
Chen J, Zhu Y, and Kaskel S (2021) Porphyrin‐based metal–organic frameworks for biomedical applications. Angewandte Chemie International Edition, 60(10): 5010-5035.
Di Carlo G, Orbelli Biroli A, Pizzotti M, et al. (2019) Efficient sunlight harvesting by A4 β-pyrrolic substituted Zn II porphyrins: a mini-review. Frontiers in Chemistry, 7:177.
Diaz D, Vidal X, Sunna A, et al. (2021) Bioengineering a light-responsive encapsulin nanoreactor: a potential tool for in vitro photodynamic therapy. ACS applied materials and interfaces, 13(7):7977-7986.
Fischer H, and Zeile K (1929) Synthese des haematoporphyrins, protoporphyrins und haemins. Justus Liebigs Annalen der Chemie, 468(1): 98-116.
Fliegl H, Dimitrova M, Berger RJ, et al. (2021) Spatial contributions to 1H NMR chemical shifts of free-base porphyrinoids. Chemistry, 3(3): 1005-1021.
Gao Y, Piradi V, Zhu X, et al. (2022) Palladium (II) and Platinum (II) Porphyrin Donors for Organic Photovoltaics. ACS Applied Energy Materials, 5(4): 4916-4925.
Gheytani S, Hassaninejad‐Darzi SK, and Taherimehr M (2020) Formaldehyde Electro‐catalytic Oxidation onto Carbon Paste Electrode Modified by MIL‐101 (Cr) Nanoparticles. Fuel Cells, 20(1): 3-16.
Girardi C, Greve J, Lamshöft M, et al. (2011) Biodegradation of ciprofloxacin in water and soil and its effects on the microbial communities. Journal of Hazardous Materials, 198: 22–30
Jaszczak E, Polkowska Ż, Narkowicz S, et al. (2017) Cyanides in the environment analysis problems and challenges. Environmental Science and Pollution Research, 24(19), 15929-15948.
Kadish KM, Guilard R, and Smith KM (Eds.). (2010) Handbook of Porphyrin Science: With Applications to Chemistry, Physics, Materials Science, Engineering, Biology and Medicine (Volumes 6-10) (Vol. 2). World Scientific.
Kim J, Oh J, Osuka A, et al. (2022) Porphyrinoids, a unique platform for exploring excited-state aromaticity. Chemical Society Reviews, 51(1): 268-292.
Kumar S, Wani MY, Arranja CT, et al. (2015) Porphyrins as nanoreactors in the carbon dioxide capture and conversion: a review. Journal of Materials Chemistry A, 3(39): 19615-19637.
Lash TD, Jones SA, and Ferrence GM (2010) Synthesis and characterization of tetraphenyl-21, 23-dideazaporphyrin: The best evidence yet that porphyrins really are the (18) annulenes of nature. Journal of the American Chemical Society, 132(37): 12786-12787.
Liang Z, Wang HY, Zheng H, et al. (2021) Porphyrin-based frameworks for oxygen electrocatalysis and catalytic reduction of carbon dioxide. Chemical Society Reviews, 50(4): 2540-2581.
Lindsey JS (1994) The synthesis of meso-substituted porphyrins. In Metalloporphyrins Catalyzed Oxidations (pp. 49-86). Dordrecht: Springer Netherlands.
Lindsey JS, Schreiman IC, Hsu HC, et al. (1987) Rothemund and Adler-Longo reactions revisited: synthesis of tetraphenylporphyrins under equilibrium conditions. The Journal of Organic Chemistry, 52(5): 827-836.
Maldonado-Carmona N, Ouk TS, Villandier N, et al. (2021) Photophysical and antibacterial properties of porphyrins encapsulated inside acetylated lignin nanoparticles. Antibiotics, 10(5): 513.
Mehraban Khaledi S, Taherimehr M and Hassaninejad-Darzi SK (2024) Porous Fe-Porphyrin as an Efficient Adsorbent for the Removal of Ciprofloxacin from Water. ACS omega, 9(14): 15950–15958.
Milroy JA (1918) Observations on some Metallic Compounds of Haematoporphyrin. Biochemical Journal, 12(4): 318.
Negut CC, Stefan-van Staden RI and van Staden JF (2020) Porphyrins-as active materials in the design of sensors. An overview. ECS Journal of Solid-State Science and Technology, 9(5): 051005.
Nguyen LM, Nguyen NTT, Nguyen TTT, et al. (2022) Occurrence, toxicity and adsorptive removal of the chloramphenicol antibiotic in water: a review. Environmental Chemistry Letters, 20(3): 1929-1963.
Qi ZL, Cheng YH, Xu Z, et al. (2020) Recent advances in porphyrin-based materials for metal ions detection. International Journal of Molecular Sciences, 21(16): 5839.
Ramasamy S, Bhagavathiachari, M, Suthanthiraraj SA, et al. (2022) Mini review on the molecular engineering of photosensitizer: Current status and prospects of metal-free/porphyrin frameworks at the interface of dye-sensitized solar cells. Dyes and Pigments, 203: 110380.
Rothemund P (1935) Formation of porphyrins from pyrrole and aldehydes. Journal of the American Chemical Society, 57(10): 2010-2011.
Senge MO, Fazekas M, Notaras EG, et al. (2007) Nonlinear optical properties of porphyrins. Advanced Materials, 19(19): 2737-2774.
Sheldon RA (1994) Oxidation catalysis by metalloporphyrins (p. 6). Dekker: New York.
Silvestri S, Fajardo AR and Iglesias BA (2022) Supported porphyrins for the photocatalytic degradation of organic contaminants in water: a review. Environmental Chemistry Letters, 20(1): 731-771.
Tahoun M, Gee CT, McCoy VE, et al. (2021) Chemistry of porphyrins in fossil plants and animals. RSC advances, 11(13): 7552-7563.
Tian J and Zhang W (2019) Synthesis, self-assembly and applications of functional polymers based on porphyrins. Progress in Polymer Science, 95: 65-117.
Vaca-Escobar K, Arregui-Almeida D and Espinoza-Montero P (2024) Chemical, ecotoxicological characteristics, environmental fate, and treatment methods applied to cyanide-containing wastewater. npj Clean Water, 7(1), 103.
Yousefnia Pasha H, Mohtasebi SS, Tabatabaeekoloor R, et al. (2021) Preparation and characterization of the plasticized polylactic acid films produced by the solvent‐casting method for food packaging applications. Journal of Food Processing and Preservation, 45(12): e16089.
Yuan P, Ruan Z, Jiang W, et al. (2018) Oxygen self-sufficient fluorinated polypeptide nanoparticles for NIR imaging-guided enhanced photodynamic therapy. Journal of Materials Chemistry B, 6(15): 2323-2331.
Zhang S, Fan Q, Xia R, et al. (2020) CO2 reduction: from homogeneous to heterogeneous electrocatalysis. Accounts of chemical research, 53(1): 255-264.
Zhao Z, Lin S, Yu Z, et al. (2023) Facile synthesis of triazine-based microporous organic network for high-efficient adsorption of flumequine and nadifloxacin: A comprehensive study on adsorption mechanisms and practical application potentials. Chemosphere, 315: 1377.
Zhou Z, Zhang L, Zhang Z, et al. (2021) Advances in photosensitizer-related design for photodynamic therapy. Asian Journal of Pharmaceutical Sciences, 16(6): 668-686.
License: Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution, and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. Visit for more details http://creativecommons.org/licenses/by/4.0/.