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Synthesis, photophysical, electrochemical, and DFT examinations of two new organic dye molecules based on phenothiazine and dibenzofuran

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Abstract

New dyes were developed and produced utilizing distinct electron donors (phenothiazine and dibenzofuran), a π-spacer, and an electron acceptor of cyanoacetohydrazide, and their structures were studied using FT-IR and NMR spectroscopy. Following the synthesis of dye molecules, the photophysical and photovoltaic characteristics were investigated using experimental and theoretical methods. The photosensitizers have been exposed to electrochemical and optical property experiments in order to study their absorption performance and also molecular orbital energies. The monochromatic optical conversion efficiency of (Z)-N-((5-(10H-phenothiazin-2-yl)furan-2-yl)methylene)-2-cyanoacetohydrazide (PFCH) was found higher than that of (Z)-2-cyano-N′-((5-(dibenzo[b,d]furan-4-yl)furan-2-yl)methylene)acetohydrazide (BFCH), with IPCEs of 58 and 64% for BFCH and PFCH, respectively. According to the photosensitizer molecular energy level diagram, the studied dye molecules have strong thermodynamically advantageous ground and excited-state oxidation potentials for electron injection into the conduction band of titanium oxide. It was observed that the ability to attract electrons correlated favorably with molecular orbital energy. While density functional theory calculations were used to examine molecule geometries, vertical electronic excitations, and frontier molecular orbitals, experimental and computed results were consistent. Natural bond orbital and nonlinear optical properties were also calculated and discussed.

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References

  1. Yella A, Lee HW, Tsao HN, Yi C, Chandiran AK, Nazeeruddin MK, Diau EWD, Yeh CY, Zakeeruddin SM, Grätzel M (2011) Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency. Science 334:629–634

    CAS  PubMed  Google Scholar 

  2. Hemavathi B, Jayadev V, Praveen RC, Pai RK, Narayanan Unni KN, Ahipa TN, Soman S, GeethaBalakrishna R (2019) Variation of the donor and acceptor in D-A–π–A based cyanopyridine dyes and its effect on dye sensitized solar cells. New J Chem 43:15673–15680

    CAS  Google Scholar 

  3. SaravanaKumaran T, Prakasam A, Anbarasan PM, Vennila P, Venkatesh G, ParveenBanu S, Sheena Mary Y (2021) New phenoxazine-based organic dyes with various acceptors for dye-sensitized solar cells: synthesis, characterization, DSSCs fabrications and DFT study. J Comput Biophys Chem 20:1–12

    Google Scholar 

  4. Mathew S, Yella A, Gao P, Humphry-Baker R, Curchod BF, Ashari-Astani N, Tavernelli I, Rothlisberger U, Nazeeruddin MK, Grätzel M (2014) Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nat Chem 6:242–247

    CAS  PubMed  Google Scholar 

  5. Yella A, Mai CL, Zakeeruddin CM, Chang SN, Hsieh CH, Yeh CY, Grätzel M (2014) Angew Chem 53:3017–3021

    Google Scholar 

  6. Amogne NY, Ayele DW, Tsigie YA (2020) Recent advances in anthocyanin dyes extracted from plants for dye sensitized solar cell. Mater Renew Sustain Energy 9:23

    Google Scholar 

  7. Zhang X, Xu Y, Giordano F, Schreier M, Pellet N, Hu Y, Yi C, Robertson N, Hua J, Zakeeruddin SM, Tian H, Grätzel M (2016) J Am Chem Soc 138:10742–10745

    CAS  PubMed  Google Scholar 

  8. Iqbal Z, Wu WQ, Huang ZS, Wang L, Kuang DB, Meier H, Cao D (2016) Trilateral π-conjugation extensions of phenothiazine based dyes enhance the photovoltaic performance of the dye-sensitized solar cells. Dyes Pigm 124:63–71

    CAS  Google Scholar 

  9. Koumura N, Wang Z-S, Mori S, Miyashita M, Suzuki E, Hara K (2008) Alkyl-functionalized organic dyes for efficient molecular photovoltaic. J Am Chem Soc 128:14256–21425

    Google Scholar 

  10. Justin Thomas KR, Kapoor N, Lee C-P, Ho K-C (2012) Organic dyes containing pyrenylamine-based cascade donor systems with different aromatic π linkers for dye-sensitized solar cells: optical, electrochemical, and device characteristics. Chem Asian J 7(4):738–750

    Google Scholar 

  11. Lee JK, Yang M (2011) Review progress in light harvesting and charge injection of dye sensitized solar cells. Mater Sci Eng B 176:1142–1160

    CAS  Google Scholar 

  12. Liu B, Zhu W, Zhang Q, Wu W, Xu M, Ning Z, Xie Y, Tian H (2009) Conveniently synthesized isophorone dyes for high efficiency dye-sensitized solar cells: tuning photovoltaic performance by structural modification of donor group in donor-π-acceptor system. Chem Commun 2:1766–1768

    Google Scholar 

  13. Horiuchi T, Miura H, Sumioka K, Uchida S (2004) High efficiency of dye-sensitized solar cells based on metal-free indoline dyes. J Am Chem Soc 126:12218–12219

    CAS  PubMed  Google Scholar 

  14. Revoju S, Biswas S, Eliasson B, Sharma GD (2018) Asymmetric triphenylamine–phenothiazine based small molecules with varying terminal acceptors for solution processed bulk-heterojunction organic solar cells. Phys Chem Chem Phys 20:6390–6640

    CAS  PubMed  Google Scholar 

  15. Slodek A, Zych D, Szafraniec-Gorol G, Gnida P, Vasylieva M, Schab-Balcerzak E (2020) Investigations of new phenothiazine-based compounds for dye-sensitized solar cells with theoretical insight. Materials 13(10):2292

    CAS  PubMed Central  Google Scholar 

  16. Bourass M, Benjelloun AT, Benzakour M, Mcharfi M, Jhilal F, Serein-Spirau F, Sotiropoulos JM, Bouachrine M (2017) DFT/TD-DFT characterization of conjugational electronic structures and spectral properties of materials based on thieno[3,2-b][1]benzothiophene for organic photovoltaic and solar cell applications. J Saudi Chem Soc 21:563–574

    CAS  Google Scholar 

  17. Khayer K, Haque T (2020) Density functional theory calculation on the structural, electronic, and optical properties of fluorene-based azo compounds. ACS Omega 5:4507–4531

    CAS  PubMed  PubMed Central  Google Scholar 

  18. Slodek A, Zych D, Golba S, Zimosz S, Gnida P, Schab-Balcerzak E (2019) Impact of the donor structure in new D–π–A systems based on indolo[3,2,1-jk]carbazoles on their thermal, electrochemical, optoelectronic and luminescence properties. J Mater Chem C 7:5830–5840

    CAS  Google Scholar 

  19. Belić J, van Beek B, Menzel JP, Buda F, Visscher L (2020) Systematic computational design and optimization of light absorbing dyes. J Phys Chem A 124:6380–6388

    PubMed  PubMed Central  Google Scholar 

  20. Abdullah G, Al-Sehemi, Shuhrah Ali S, Allami AbulKalam (2020) Design and synthesis of organic dyes with various donor groups: promising dyes for dye-sensitized solar cells. Bull Mater Sci 43:224

    Google Scholar 

  21. Park JM, Jung CY, Wang Y, Choi HD, Park SJ, Ou P, Jang WD, Jaung JY (2019) Effect of additional phenothiazine donor and thiophene π-bridge on photovoltaic performance of quinoxaline cored photosensitizers. Dyes Pigms. 170:107568

    CAS  Google Scholar 

  22. Huang ZS, Meier H, Cao D (2016) Phenothiazine-based dyes for efficient dye-sensitized solar cells. J Mater Chem C 4:2404–2426

    CAS  Google Scholar 

  23. Buene AF, Uggerud N, Economopoulos SP, Gautun OR, Hoff BH (2018) Dyes Pigms 151:263–271

    CAS  Google Scholar 

  24. Ahmad S, Guillen E, Kavan L, Grätzel M, Nazeeruddin MK (2013) Metal free sensitizer and catalyst for dye sensitized solar cells. Energy Environ Sci 6:3439–3466

    CAS  Google Scholar 

  25. Zhou H, Ji JM, Kang SH, Kim MS, Lee HS, Kim CH, Kim HK (2019) Molecular design and synthesis of D–π–A structured porphyrin dyes with various acceptor units for dye-sensitized solar cells. J Mater Chem C 7:2843–2852

    CAS  Google Scholar 

  26. Velu S, Muniyasamy H, Ayyanar S, Maniarasu S, Veerappan G, Sepperumal M (2019) synthesis of organic sensitizers containing carbazole and triphenylamine π-bridged moiety for dye-sensitized solar cells. J Iran Chem Soc 16:1923–1937

    CAS  Google Scholar 

  27. Kim SH, Kim HW, Sakong C, Namgoong J, Park SW, Ko MK, Hyuk Lee C, Lee WI, Kim JP (2011) Effect of five-membered heteroaromatic linkers to the performance of phenothiazine-based dye-sensitized solar cells. Org Lett 13:5784–5787

    CAS  PubMed  Google Scholar 

  28. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Asegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Ioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, AlLaham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2009) Gaussian 03, Revision E.01. Gaussian Inc., Pittsburgh, B.A. 2000. Walliford CT, 121:150-166

  29. Scott AP, Radom L (1996) Harmonic vibrational frequencies: an evaluation of Hartree—Fock, Moller—Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors. J Phys Chem 100:16502–16513

    CAS  Google Scholar 

  30. Islam N, Kaya S (2018) Conceptual density functional theory and its application in the chemical domain. CRC Press

    Google Scholar 

  31. Koopmans T (1934) über Die Zuordnung Von Wellenfunktionen Und Eigenwerten Zu Den Einzelnen Elektronen Eines Atoms. Physica 1:104–113

    Google Scholar 

  32. Pearson RG (1999) Maximum chemical and physical hardness. J Chem Educ 76:267

    CAS  Google Scholar 

  33. Gazquez JL, Cedillo A, Vela A (2007) Electrodonating and electroaccepting powers. J Phys Chem A 111:1966–1970

    CAS  PubMed  Google Scholar 

  34. Palanisamy SP, Maheswaran G, GeethaSelvarani A, Kamal C, Venkatesh G (2018) Ricinus communis – a green extract for the improvement of anti-corrosion and mechanical properties of reinforcing steel in concrete in chloride media. J Build Eng 19:376–383

    Google Scholar 

  35. SaravanaKumaran T, Prakasam A, Venkatesh G, Kamal C, Sheena Mary Y, ParveenBanu S, Vennila P, Shyma Mary Y (2020) Synthesis, spectral characterizations, molecular geometries and electronic properties of phenothiazine based organic dyes for dye-sensitized solar cells. Z Phys Chem. https://doi.org/10.1515/zpch-2020-1732

    Article  Google Scholar 

  36. Zanjanchi F, Beheshtian J (2018) Natural pigments in dye-sensitized solar cell (DSSC): A DFT-TDDFT study. J Iran Chem Soc 16:795–805. https://doi.org/10.1007/s13738-018-1561-2

    Article  CAS  Google Scholar 

  37. SaravanaKumaran T, Prakasam A, Vennila P, ParveenBanu S, Venkatesh G (2021) New carbazole-based organic dyes with various acceptors for dye-sensitized solar cells: synthesis, characterization, DSSCs fabrications and DFT study. Asian J Chem 33:1541–1550

    Google Scholar 

  38. Harikrishnan M, Sadhasivam V, Siva A, Anandan S, Subbiah V, Murugesan S (2019) Energy level tuning of novel star-shaped D−π–D–A-based metal-free organic dyes for solar cell application. J Phys Chem C 123:21959–21968

    CAS  Google Scholar 

  39. Sun C, Li Y, Qi D, Li H (2016) Optical and electrical properties of purpurin and alizarin complexone as sensitizers for dye-sensitized solar cells. J Mater Sci: Mater Electron 27:8027–8039

    CAS  Google Scholar 

  40. Periyasamy K, Sakthivel P, Vennila P, Anbarasan PM, Venkatesh G, Sheena Mary Y (2021) Novel D-π-A phenothiazine and dibenzofuran organic dyes with simple structures for efficient dye-sensitized solar cells. J Photochem Photobiol A 413:113269

    CAS  Google Scholar 

  41. Batzill M (2011) Fundamental aspects of surface engineering of transition metal oxide photocatalysts. Energy Environm Sci 4:3275–3286

    CAS  Google Scholar 

  42. Pan J, Liu G, Lu GQ, Cheng HM (2011) On the true photoreactivity order of 001}, {010 and 101 facets of anatase TiO2 crystals. Angew Chem Int Ed 50:2133–2137

    CAS  Google Scholar 

  43. Zhang We Li, Yang Xichuan, Wang Weihan, Gurzadyan Gagik G, Li Jiajia, Li Xiaoxin, An Jincheng, Ze Yu, Wang Haoxin, Cai Bin, Hagfeldt Anders, Sun Licheng (2019) 13.6% efficient organic dye-sensitized solar cells by minimizing energy losses of the excited state. ACS Energy Lett 4:943–95

    CAS  Google Scholar 

  44. Zeng K, Chen Y, Zhu W-H, Tian He, Xie Y (2020) Efficient solar cells based on concerted companion dyes containing two complementary components: an alternative approach for cosensitization. J Am Chem Soc 142:5154–5161

    CAS  PubMed  Google Scholar 

  45. Ji J-M, Zhou H, Kim HK (2018) Rational design criteria for D–π–A structured organic and porphyrin sensitizers for highly efficient dye-sensitized solar cells. J Mater Chem A 6:14518–14545

    CAS  Google Scholar 

  46. Athira M. John, Renjith Thomas, Sreeja P. Balakrishnan, Nabil Al-Zaqri, Ali Alsalme, Ismail Warad. Diazo-pyrazole analogues as photosensitizers in dye sensitised solar cells: tuning for a better photovoltaic efficiency using a new modelling strategy using experimental and computational data. Zeitschrift für Physikalische Chemie. https://doi.org/10.1515/zpch-2020-1722

  47. Venkatesh G, Kamal C, Vennila P, Govindaraju M, Sheena Mary Y, Armakovic S, Armakovic SJ, Kaya S, YohannanPanicker C (2018) Molecular dynamic simulations, ALIE surface, Fukui functions geometrical, molecular docking and vibrational spectra studies of tetra chloro p and m-xylene. J Mol Struct 1171:253–267

    CAS  Google Scholar 

  48. Pearson RG (1963) Hard and soft acids and bases. J Am Chem Soc 85:3533–3539

    CAS  Google Scholar 

  49. Saha R, Pan S, Chattaraj PK (2016) Molecules statistical significance of the maximum hardness principle applied to some selected chemical reactions. Molecules 21:1477

    PubMed Central  Google Scholar 

  50. Ghanty TK, Ghosh SK (2000) Molecular hardness, polarizability and valency variation of formamide and thioformamide on internal rotation: a density functional study. J Phys Chem A 104:2975–2979

    CAS  Google Scholar 

  51. Chattaraj PK, Sarkar U, Roy DR (2006) Electrophilicity index. Chem Rev 106:2065–2091

    CAS  PubMed  Google Scholar 

  52. Chamorro E, Chattaraj PK, Fuentealba P (2003) Variation of the electrophilicity index along the reaction path. J Phys Chem A 107:7068–7072

    CAS  PubMed  Google Scholar 

  53. von Szentpály László, Kaya Savaş, Karakuş Nihat (2020) Why and when is electrophilicity minimized? New theorems and guiding rules. Am J Phys Chem 124:10897–10908

    Google Scholar 

  54. Vennila P, Govindaraju M, Venkatesh G, Kamal C (2016) Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations. J Mol Struct 1111:151

    CAS  Google Scholar 

  55. Weinhold F, Landis CR, Glendening ED (2016) What is NBO analysis and how is it useful? Int Rev in Phys Chem 35:399

    CAS  Google Scholar 

  56. Venkatesh G, Govindaraju M, Kamal C, Vennila P, Kaya S (2017) Structural, electronic and optical properties of 2,5 dichloro-p-xylene: experimental and theoretical calculations using DFT method. RSC Adv 7:1401

    CAS  Google Scholar 

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Acknowledgements

The authors would like to express their gratitude to Gandhigram Rural University and SAIF Chennai for providing spectral and electrochemical resources.

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Authors and Affiliations

  1. Department of Physics, Vaigai Arts and Science Women’s College, Salem, 636 111, India

    K. Periyasamy

  2. Department of Physics, Selvamm Arts and Science College, Namakkal, 637 003, India

    P. Sakthivel

  3. Department of Chemistry, MMCAS, Rasipuram, Tamil Nadu, 637408, India

    G. Venkatesh

  4. Department of Physics, Periyar University, Salem, 636 011, India

    P. M. Anbarasan

  5. Department of Chemistry, Thiruvalluvar Government Arts College, Rasipuram, 637401, India

    P. Vennila

  6. Researcher, Thushara, Neethinagar-64, Kollam, Kerala, India

    Y. Sheena Mary

  7. Department of Chemistry, Cumhuriyet University, Sivas, 58140, Turkey

    S. Kaya

  8. Department of Chemistry, Faculty of Science, Cumhuriyet University, Sivas, 58140, Turkey

    Sultan Erkan

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  1. K. Periyasamy
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  2. P. Sakthivel
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  8. Sultan Erkan
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Contributions

K. Periyasamy: experimental, DFT studies, and manuscript writing.

P. Sakthivel: supervision, manuscript preparation, and data analysis.

G. Venkatesh: manuscript draft correction and method development and standardization.

P.M. Anbarasan: software and electrochemical data analysis.

P. Vennila: validation curation of data and method development.

Y. Sheena Mary: conceiving of the problem.

S. Kaya: FMO calculation.

Sultan Erkan: manuscript draft correction.

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Correspondence to K. Periyasamy.

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Periyasamy, K., Sakthivel, P., Venkatesh, G. et al. Synthesis, photophysical, electrochemical, and DFT examinations of two new organic dye molecules based on phenothiazine and dibenzofuran. J Mol Model 28, 34 (2022). https://doi.org/10.1007/s00894-022-05026-w

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