STRUCTURAL STABILITY AND SUBSTITUENT EFFECTS ON THE PHOTOPHYSICAL PROPERTIES OF THIOANISOLE EXPLORED BY EXCITED-STATE DYNAMIC SIMULATIONS
DOI:
https://doi.org/10.55766/sujst9130Keywords:
On-the-fly dynamic simulations, Thioanisole, B3LYP, TD-B3LYP, Substituent effectsAbstract
The photophysical properties of thioanisole (SCH3) and its derivatives as a representative system for investigating aryl sulfides were explored by TD-DFT using the B3LYP functional. Thioanisole appears in a variety of chemical applications due to its structural and reactive properties such as in dyes, drugs, and materials. Our investigations focus on the structural, photophysical, and dynamic properties influenced by substituents (F and Cl) on absorption and emission spectra. The electronic transition mainly corresponds to S₀→S₂ (π→σ*) with excitation energies of 5.11 eV and 5.02 eV for SCH₃F and SCH₃Cl, respectively. The dynamic simulations on the first-excited state provide additional insights that complement those obtained from static calculations. The fluorescence spectrum of SCH3F typically shows a blue shift, while the fluorescence spectrum of SCH3Cl displays a red shift compared to SCH3. These findings indicate that the inductive effect plays a crucial role in structural stability, particularly influencing internal conversion during the dynamics, which may lead to a reduced fluorescence intensity.
References
Ahlrichs, R., Bär, M., Häser, M., Horn, H., and Kölmel, C. (1989). Electronic structure calculations on workstation computers: The program system turbomole. Chemical Physics Letters, 162(3):165-169. https://doi.org/https://doi.org/10.1016/0009-2614(89)85118-8
Andrusenko, I., Hall, C.L., Mugnaioli, E., Potticary, J., Hall, S.R., Schmidt, W., Gao, S., Zhao, K., Marom, N., and Gemmi, M. (2023). True molecular conformation and structure determination by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applications. IUCrJ, 10(1):131-142. https://doi.org/10.1107/s205225252201154x
Barbatti, M., Granucci, G., Persico, M., Ruckenbauer, M., Vazdar, M., Eckert-Maksić, M., and Lischka, H. (2007). The on-the-fly surface-hopping program system Newton-X: Application to ab initio simulation of the nonadiabatic photodynamics of benchmark systems. Journal of Photochemistry and Photobiology A: Chemistry, 190(2):228-240. https://doi.org/https://doi.org/10.1016/j.jphotochem.2006.12.008
Bossa, M., Morpurgo, S., and Stranges, S. (2002). The use of ab initio and DFT calculations in the interpretation of ultraviolet photoelectron spectra: the rotational isomerism of anisole and thioanisole as a case study. Journal of Molecular Structure: THEOCHEM, 618(1): 155-164. https://doi.org/https://doi.org/10.1016/S0166-1280(02)00469-4
Brédas, J.-L., Cornil, J., Beljonne, D., dos Santos, D.A., and Shuai, Z. (1999). Excited-State Electronic Structure of Conjugated Oligomers and Polymers: A Quantum-Chemical Approach to Optical Phenomena. Accounts of Chemical Research, 32(3):267-276. https://doi.org/10.1021/ar9800338
Bzhezovskii, V.M., and Kapustin, E.G. (2002). Intramolecular Interactions in Anisole, Thioanisole, and Selenoanisole. Application of Natural Bond Orbitals Method. Russian Journal of Organic Chemistry, 38(4):564-572. https://doi.org/10.1023/A:1016559525299
Bzhezovskii, V.M., Kapustin, E.G., Chura, M.B., and Shermolovich, Y.G. (2004). An ab initio quantum-chemical study of the compounds HC≡CXCH3 (X = O, S, Se). Russian Journal of General Chemistry, 74(11):1,697-1,701. https://doi.org/10.1007/s11176-005-0085-5
Daengngern, R., Prommin, C., Rungrotmongkol, T., Promarak, V., Wolschann, P., and Kungwan, N. (2016). Theoretical investigation of 2-(iminomethyl)phenol in the gas phase as a prototype of ultrafast excited-state intramolecular proton transfer. Chemical Physics Letters, 657:113-118. https://doi.org/https://doi.org/10.1016/j.cplett.2016.05.065
Dragan, A.I., Bishop, E.S., Casas-Finet, J.R., Strouse, R.J., McGivney, J., Schenerman, M.A., and Geddes, C.D. (2012). Distance Dependence of Metal-Enhanced Fluorescence. Plasmonics, 7(4):739-744. https://doi.org/10.1007/s11468-012-9366-0
Fu, M., Xiao, Y., Qian, X., Zhao, D., and Xu, Y. (2008). A design concept of long-wavelength fluorescent analogs of rhodamine dyes: Replacement of oxygen with silicon atom. Chemical communications (Cambridge, England), 15:1,780-1,782. https://doi.org/10.1039/b718544h
Gellini, C., Moroni, L., and Muniz-Miranda, M. (2002). High Overtones of the C-H Stretching Vibrations in Anisole and Thioanisole. The Journal of Physical Chemistry A, 106(46):10,999-11,007. https://doi.org/10.1021/jp020691g
Hillers-Bendtsen, A., Kjeldal, F., Ree, N., Matito, E., and Mikkelsen, K. (2022). Excited State Dynamics and Conjugation Effects of the Photoisomerization Reactions of Dihydroazulene. Physical Chemistry Chemical Physics, 24. https://doi.org/10.1039/D2CP02706B
Hospital, A., Goñi, J.R., Orozco, M., and Gelpí, J.L. (2015). Molecular dynamics simulations: advances and applications. Adv Appl Bioinform Chem, 8:37-47. https://doi.org/10.2147/aabc.S70333
Ibnaouf, K., Elzupir, A., AlSalhi, M., and Alaamer, A. (2018). Influence of functional groups on the photophysical properties of dimethylamino chalcones as laser dyes. Optical Materials, 76:216-221. https://doi.org/10.1016/j.optmat.2017.12.034
Jun, W., Wu, Q., Xu, Y., Yu, C., Wei, Y., Mu, X., Hao, E., and Jiao, L. (2024). Synthesis, structure and photophysical properties of near-infrared 3,5-diarylbenzoBODIPY fluorophores. RSC Advances, 6:52180.
https://doi.org/10.1039/C6RA04412C
Kim, S.-Y., Lee, J., Kim, S.K., and Choi, Y.S. (2016). Nonplanar structure of C6H5SCF3 facilitates πσ∗-mediated photodissociation reaction on the S1 state. Chemical Physics Letters, 659:43-47. https://doi.org/https://doi.org/10.1016/j.cplett.2016.06.083
Kungwan, N., Plasser, F., Aquino, A.J.A., Barbatti, M., Wolschann, P., and Lischka, H. (2012). The effect of hydrogen bonding on the excited-state proton transfer in 2-(2′-hydroxyphenyl)benzothiazole: a TDDFT molecular dynamics study [10.1039/C2CP23905A]. Physical Chemistry Chemical Physics, 14(25):9,016-9,025. https://doi.org/10.1039/C2CP23905A
Lee, J.-H., Wang, P.-S., Park, H.-D., Wu, C.-I., and Kim, J.-J. (2011). A high performance inverted organic light emitting diode using an electron transporting material with low energy barrier for electron injection. Organic Electronics, 12(11):1,763-1,767. https://doi.org/https://doi.org/10.1016/j.orgel.2011.07.015
Malongwe, J.K., Nachtigallová, D., Corrochano, P., and Klán, P. (2016). Spectroscopic Properties of Anisole at the Air-Ice Interface: A Combined Experimental-Computational Approach. Langmuir, 32(23):5,755-5,764. https://doi.org/10.1021/acs.langmuir.6b01187
Manoharan, M., Proft, F., and Geerlings, P. (2000). A computational study of aromaticity-controlled Diels-Alder reactions. Journal of The Chemical Society-perkin Transactions 2 - J CHEM SOC PERKIN TRANS 2:1,767-1,773. https://doi.org/10.1039/b002344m
Nagasaka-Hoshino, M., Isozaki, T., Suzuki, T., Ichimura, T., and Kawauchi, S. (2008). Molecular structure of jet-cooled thioanisole studied by laser-induced fluorescence spectroscopy and ab initio calculations: Planar and/or perpendicular conformation? Chemical Physics Letters, 457(1):58-61. https://doi.org/https://doi.org/10.1016/j.cplett.2008.04.040
Schäfer, A., Horn, H., and Ahlrichs, R. (1992). Fully optimized contracted Gaussian basis sets for atoms Li to Kr. The Journal of Chemical Physics, 97(4):2,571-2,577. https://doi.org/10.1063/1.463096
Shahzad, A., Köhler, G., Knapp, M., Gaubitzer, E., Puchinger, M., and Edetsberger, M. (2009). Emerging applications of fluorescence spectroscopy in medical microbiology field. Journal of Translational Medicine, 7(1):99. https://doi.org/10.1186/1479-5876-7-99
Sheldon, C., Paier, J., Usvyat, D., and Sauer, J. (2024). Hybrid RPA:DFT Approach for Adsorption on Transition Metal Surfaces: Methane and Ethane on Platinum (111). Journal of Chemical Theory and Computation, 20(5):2,219-2,227. https://doi.org/10.1021/acs.jctc.3c01308
Stephens, P.J., Devlin, F.J., Chabalowski, C.F., and Frisch, M.J. (1994). Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields. The Journal of Physical Chemistry, 98(45):11,623-11,627. https://doi.org/10.1021/j100096a001
Valeur, B., & Berberan-Santos, M. N. (2013). Molecular fluorescence: principles and applications. John Wiley & Sons.
Yamakita, Y., Isogai, Y., and Ohno, K. (2006). Large Raman-scattering activities for the low-frequency modes of substituted benzenes: induced polarizability and stereo-specific ring-substituent interactions. J Chem Phys, 124(10):104301. https://doi.org/10.1063/1.2163344
Yang, Y. (2016). Chapter 3 - Peptide Global Deprotection/Scavenger-Induced Side Reactions. In Y. Yang (Ed.), Side Reactions in Peptide Synthesis (pp. 43-75). Academic Press. https://doi.org/https://doi.org/10.1016/B978-0-12-801009-9.00003-3
Zhang, S., Liu, Q., Cheng, H., and Zeng, F. (2015). Combined experimental and theoretical investigation of interactions between kaolinite inner surface and intercalated dimethyl sulfoxide. Applied Surface Science, 331. https://doi.org/10.1016/j.apsusc.2015.01.019
Zhang, Z., Li, M., Hou, G.L., and Gao, H. (2022). Substitution-induced Nonplanarity of 3-Fluorothioanisole in the First Electronically Excited State. J Phys Chem A, 126(16):2,541-2,550. https://doi.org/10.1021/acs.jpca.2c01234
