+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Molecular model of the ring-opening and ring-closure reaction of a fluorinated indolylfulgide



Molecular model of the ring-opening and ring-closure reaction of a fluorinated indolylfulgide



Journal of Physical Chemistry. a 116(43): 10518-10528



A combination of experimental and theoretical techniques is used to study the photoinduced ring-opening/closure of a trifluoromethyl-indolylfulgide. Time-resolved UV/vis pump and IR probe measurements are performed in the subpicosecond to 50 ps time range. Probing in the mid-IR between 1200 and 1900 cm(-1) provides mode-specific dynamics and reveals photochemical reaction dynamics as well as the presence of a noncyclizable conformer. Ring-opening occurs with about 3 ps. Experiments on the open isomer confirm that the ring-closure occurs on the subpicosecond time scale. They also show a 10 ps transient that can be assigned to internal conversion of a noncyclizable conformer. Quantum chemical calculations with multireference methods are used to explore the complex potential energy landscape in the excited electronic state showing paths for ring-opening and closure reactions as well as for competing side-reactions. The calculations reveal that photoexcitation induces a charge transfer from the indole to the anhydride. The same charge transfer drives the system toward a low-energy conical intersection seam spreading from the closed to the open ring side and is responsible for the ultrafast relaxation to the ground state. The ultrafast photoreactivity comes at the expense of selectivity.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 054446664

Download citation: RISBibTeXText

PMID: 23020139

DOI: 10.1021/jp307437f


Related references

Ring-opening reaction of a trifluorinated indolylfulgide: mode-specific photochemistry after pre-excitation. Physical Chemistry Chemical Physics 11(25): 5019-5027, 2009

Ring Expansion of Diazo-Functionalized 4-Hydroxycyclobutenone: Catalytic Ring Opening and Recyclization to 2(5H)-Furanone/Cyclopentenedione and Thermal 4pi-8pi Electrocyclic Ring Opening-Closure to Diazepinedione. Journal of Organic Chemistry 64(3): 707-712, 2001

A new approach to the nazarov reaction via sequential electrocyclic ring opening and ring closure. Journal of the American Chemical Society 128(29): 9348-9349, 2006

Ring Opening-Ring Closure of 4-Phenyl-1,2-dithiole-3-thione: Reaction with α,β-Unsaturated Nitriles. Phosphorus Sulfur and Silicon and the Related Elements 178(10): 2255-2261, 2003

An acid catalyzed reversible ring-opening/ring-closure reaction involving a cyano-rhodamine spirolactam. Organic and Biomolecular Chemistry 11(11): 1805-1809, 2014

Simple assembly of polysubstituted pyrazoles and isoxazoles via ring closure-ring opening domino reaction of 3-acyl-4,5-dihydrofurans with hydrazines and hydroxylamine. Organic and Biomolecular Chemistry 14(10): 2905-2915, 2016

Novel reaction of 5 nitro or carbamoyl uracil derivatives with amines thermal exchange reaction of n 1 portion of the uracils for amines via ring opening and ring closure processes. Tetrahedron Letters 27(28): 3263-3266, 1986

Furan ring opening: Indole ring closure: A new modification of the Reissert reaction for indole synthesis. Tetrahedron Letters 42(10): 2031-2033, 4 March, 2001

On the condensed phase ring-closure of vinylheptafulvalene and ring-opening of gaseous dihydroazulene. Journal of Physical Chemistry. a 117(16): 3340-3347, 2013

"Ring opening-ring closure" strategy for the synthesis of aryl-C-glycosides. Journal of Organic Chemistry 79(10): 4676-4686, 2015

A One-Pot Ring-Opening/Ring-Closure Sequence for the Synthesis of Polycyclic Spirooxindoles. Chemistry 2019, 2019

Oxidative ring closure and metal triggered ring opening: syntheses of macrocyclic and linear hexapyrroles. Organic Letters 16(24): 6354-6357, 2015

Palladium-catalyzed multistep reactions involving ring closure of 2-iodophenoxyallenes and ring opening of bicyclic alkenes. Organic Letters 8(4): 621-623, 2006

Using Ring Strain to Control 4π-Electrocyclization Reactions: Torquoselectivity in Ring Closing of Medium-Ring Dienes and Ring Opening of Bicyclic Cyclobutenes. Journal of Organic Chemistry 82(9): 4613-4624, 2017

Furan ring opening-pyrrole ring closure: a new synthetic route to aryl(heteroaryl)-annulated pyrrolo[1,2-a][1,4]diazepines. Organic and Biomolecular Chemistry 8(14): 3316-3327, 2010