Toward Designed Singlet Fission: Electronic States and Photophysics of 1,3-Diphenylisobenzofuran

Journal Article · Mon Dec 21 04:00:00 EST 2009 · Journal of Physical Chemistry A

OSTI ID:1040375

Schwerin, A F; Miller, J; Johnson, J C; Smith, M B; Sreearunothai, P; Popovic, D; Cerny, J; Havlas, Z; Paci, I; Akdag, A; MacLeod, M K; Chen, X; David, D E; Ratner, M A; Nozik, A J; Mich, J

Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest as a model compound in studies of singlet fission. For the ground state of 1 and of its radical cation (1{sup +{sm_bullet}}) and anion (1{sup -{sm_bullet}}), we report the UV-visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. These results were used to identify a series of singlet excited states. For the first excited singlet and triplet states of 1, the transient visible absorption spectra, S{sub 1} {yields} S{sub x} and sensitized T{sub 1} {yields} T{sub x}, and single exponential lifetimes, {tau}{sub F} = {approx} 5.3 ns and {tau}{sub T} = {approx}200 {mu}s, are reported. The spectra and lifetimes of S{sub 1} {yields} S{sub 0} fluorescence and sensitized T{sub 1} {yields} T{sub x} absorption of 1 were obtained in a series of solvents, as was the fluorescence quantum yield, {Phi}{sub F} = 0.95-0.99. No phosphorescence has been detected. The first triplet excitation energy of solid 1 (11,400 cm{sup -1}) was obtained by electron energy loss spectroscopy, in agreement with previously reported solution values. The fluorescence excitation spectrum suggests an onset of a nonradiative channel at {approx} 37,000 cm{sup -1}. Excitation energies and relative transition intensities are in agreement with those of ab initio (CC2) calculations after an empirical 3000 cm{sup -1} adjustment of the initial state energy to correct differentially for a better quality description of the initial relative to the terminal state of an absorption transition. The interpretation of the MCD spectrum used the semiempirical PPP method, whose results for the S{sub 0} {yields} S{sub x} spectrum require no empirical adjustment and are otherwise nearly identical with the CC2 results in all respects including the detailed nature of the electronic excitation. The ground state geometry of 1 was also calculated by the MP2, B3LYP, and CAS methods. The calculations provided a prediction of changes of molecular geometry upon excitation or ionization and permitted an interpretation of the spectra in terms of molecular orbitals involved. Computations suggest that 1 can exist as two nearly isoenergetic conformers of C{sub 2} or C{sub s} symmetry. Linear dichroism measurements in stretched polyethylene provide evidence for their existence and show that they orient to different degrees, permitting a separation of their spectra in the region of the purely polarized first absorption band. Their excitation energies are nearly identical, but the Franck-Condon envelopes of their first transition differ to a surprising degree.

• Research Organization: Brookhaven National Laboratory (BNL) Laser Electron Accelerator Facility (LEAF)
• Sponsoring Organization: USDOE SC OFFICE OF SCIENCE (SC)
• DOE Contract Number: AC02-98CH10886
• OSTI ID: 1040375
• Report Number(s): BNL--91206-2010-JA; KC0301010
• Journal Information: Journal of Physical Chemistry A, Journal Name: Journal of Physical Chemistry A Journal Issue: 3 Vol. 114
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
ABSORPTION
ABSORPTION SPECTRA
DICHROISM
ENERGY-LOSS SPECTROSCOPY
EXCITATION
EXCITED STATES
FISSION
FLUORESCENCE
GEOMETRY
GROUND STATES
IONIZATION
MAGNETIC CIRCULAR DICHROISM
MOLECULAR STRUCTURE
MONOCRYSTALS
PHOSPHORESCENCE
POLARIZATION
POLYETHYLENES
RADICALS
SOLVENTS
SPECTRA
laser electron accelerator facility
radical anion
radical cation
single fission