Theoretical and experimental studies on the chemiexcitation efficiency of cyclic peroxide decomposition

• Grant number: 15/02314-8
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Effective date (Start): July 01, 2015
• Effective date (End): June 30, 2017
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Acordo de Cooperação: Coordination of Improvement of Higher Education Personnel (CAPES)
• Principal Investigator: Joséf Wilhelm Baader
• Grantee: Pooria Farahani
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil

Abstract

The general aim of this project is a mechanistic study of organic chemiluminescence reactions, currently utilised in a wide variety of analytical applications, using a combination of experimental and theoretical approaches. The candidate has a very good knowledge of the theoretical methodology obtained during his PhD studies at the Theoretical Chemistry Programme of Ångström Laboratory, Uppsala University, Uppsala, Sweden and he will be involved also in experimental studies on several chemiluminescence systems investigated by the Organic Chemiluminescence Laboratory at the IQUSP. Applying the theoretical strategies using the multiconfigurational CASSCF/CASPT2 approach, the mechanisms of several chemiluminescence transformation (unimolecular 1,2-dioxetane decomposition, catalyzed peroxide decomposition, induced phenoxyl-substituted 1,2-dioxetane decomposition and peroxyoxalate reaction) will be studied, with the objective to elucidate the factors necessary for efficient electronically excited state formation. The results of these theoretical calculations will be compared to the experimental data on these chemiluminescence systems available in the São Paulo research group. Additionally, the candidate will have the opportunity to apply the experimental methodology of mechanistic chemiluminescence research, dominated by the São Paulo research group, to the study of chemiluminescence systems, selected on the basis of the theoretical studies. (AU)

Scientific publications

(7)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

FARAHANI, POORIA; BAADER, WILHELM J.. Unimolecular Decomposition Mechanism of 1,2-Dioxetanedione: Concerted or Biradical? That is the Question!. Journal of Physical Chemistry A, v. 121, n. 6, p. 1189-1194, FEB 16 2017. (14/22136-4, 15/02314-8)

ZENDEHDEL, MAHMOUD; NIA, NARGES YAGHOOBI; NASR-ESFAHANI, MOJTABA; FARAHANI, POORIA; KARBASCHI, MOHAMAD REZA. A combined computational and experimental study on the hydrogen bonding with chloride ion in a crab-claw like site of a new chromium Schiff base complex. Inorganica Chimica Acta, v. 447, p. 150-161, JUN 1 2016. (15/02314-8)

FARAHANI, POORIA; OLIVEIRA, MARCELO A.; GALVAN, IGNACIO FDEZ; BAADER, WILHELM J.. A combined theoretical and experimental study on the mechanism of spiro-adamantyl-1,2-dioxetanone decomposition. RSC ADVANCES, v. 7, n. 28, p. 17462-17472, 2017. (14/22136-4, 15/02314-8)

PUSCH, STEFAN; TROESTER, ANDREAS; LEFRANCOIS, DANIEL; FARAHANI, POORIA; DREUW, ANDREAS; BACH, THORSTEN; OPATZ, TILL. Mechanism and cis/trans Selectivity of Vinylogous Nazarov-type [6 pi] Photocyclizationst. Journal of Organic Chemistry, v. 83, n. 2, p. 964-972, JAN 19 2018. (15/02314-8)

BASTOS, ERICK LEITE; FARAHANI, POORIA; BECHARA, ETELVINO J. H.; BAADER, WILHELM JOSEF. Four-membered cyclic peroxides: Carriers of chemical energy. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, v. 30, n. 9, SI, SEP 2017. (14/22136-4, 16/21445-9, 15/02314-8)

VACHER, MORGANE; FARAHANI, POORIA; VALENTINI, ALESSIO; FRUTOS, LUIS MANUEL; KARLSSON, HANS O.; GALVAN, IGNACIO FDEZ.; LINDH, ROLAND. How Do Methyl Groups Enhance the Triplet Chemiexcitation Yield of Dioxetane?. Journal of Physical Chemistry Letters, v. 8, n. 16, p. 3790-3794, AUG 17 2017. (15/02314-8)

BASTOS, ERICK LEITE; FARAHANI, POORIA; BECHARA, ETELVINO J. H.; BAADER, WILHELM JOSEF. Four-membered cyclic peroxides: Carriers of chemical energy. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, v. 30, n. 9, p. 18-pg., 2017-09-01. (15/02314-8, 16/21445-9, 14/22136-4)