The First in Situ Direct Observation of the Light-Induced Radical Pair from a Hexaarylbiimidazolyl Derivative by X-ray Crystallography

Michihisa Kawano; Tomokatsu Sano; Jiro Abe; Yuji Ohashi

doi:10.1021/ja9903173

journal article Aug 12, 1999

The First in Situ Direct Observation of the Light-Induced Radical Pair from a Hexaarylbiimidazolyl Derivative by X-ray Crystallography

Michihisa Kawano Tomokatsu Sano Jiro Abe

Yuji Ohashi

Journal of the American Chemical Society Vol. 121 No. 35 pp. 8106-8107 · American Chemical Society (ACS)

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o-Cl-HABI was prepared according to the ref 2b. The diffraction data ofo-Cl-HABI was measured before irradiation and after warming a RP-contained crystal to room temperature to confirm the reversible structural changes. The following data set was measured using a thermally regenerated initial-state crystal. With irradiation and several temperature changes, the X-ray data showed no significant crystal decay. C42H28Cl2N4, MW = 659.58, orthorhombic, space groupPbca, λ(Mo Kα) = 0.71073 Å,T= 103(2) K,a= 16.7314(2) Å,b= 17.3877(3) Å,c= 46.0307(6) Å,V= 13391.3(3) Å3,Z= 16,dcalcd= 1.309 Mg/m3. Anisotropic least-squares refinement (865 parameters) on 19426 independent merged reflections (Rint= 0.0413) converged atwR2(F2) = 0.1010 for all data;R1(F) = 0.0409 for 14796 observed data (I> 2σ(I)), GOF = 1.005.

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A thin plate single crystal (320 × 300 × 80 μm) ofo-Cl-HABI was gradually cooled below 103 K and irradiated with a high-pressure mercury lamp for 20 min. C42H28Cl2N4, MW = 659.58, orthorhombic, space groupPbca, λ(Mo Kα) = 0.71073 Å,T= 103(2) K,a= 16.6975(3) Å,b= 17.3715(3) Å,c= 45.9434(3) Å,V= 13326.4(3) Å3,Z= 16,dcalcd= 1.315 Mg/m3. During the X-ray diffraction measurement below 103 K, no decay was observed. Isotropic and anisotropic least-squares refinement (632 parameters/90 restraints) on 19111 independent merged reflections (Rint= 0.0588) converged atwR2(F2) = 0.1210 for all data;R1(F) = 0.0535 for 14328 observed data (I> 2σ(I)), GOF = 1.080. Since the phenyl groups of RP with relatively low populations are severely overlapped with those of the dimer, they are restrained, and the thermal parameters of B are fixed by using the dimer's structural parameters presented in ref 7.

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The molecular structure has been fully optimized at the DFT/Becke3LYP level with the 6-31G basis set. The transition energies were calculated based on the semiempirical CNDO/S Hamiltonian with configuration interaction wave functions.

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Details

Published: Aug 12, 1999
Vol/Issue: 121(35)
Pages: 8106-8107

Authors

M

Michihisa Kawano

CREST, Japan Science and Technology Corporation, and Department of Chemistry Tokyo Institute of Technology, Tokyo 152-8551 Japan Department of Photo-Optical Engineering Tokyo Institute of Polytechnics Kanagawa 243-0297 Japan

T

Tomokatsu Sano

CREST, Japan Science and Technology Corporation, and Department of Chemistry Tokyo Institute of Technology, Tokyo 152-8551 Japan Department of Photo-Optical Engineering Tokyo Institute of Polytechnics Kanagawa 243-0297 Japan

J

Jiro Abe

CREST, Japan Science and Technology Corporation, and Department of Chemistry Tokyo Institute of Technology, Tokyo 152-8551 Japan Department of Photo-Optical Engineering Tokyo Institute of Polytechnics Kanagawa 243-0297 Japan

Y

Yuji Ohashi

CREST, Japan Science and Technology Corporation, and Department of Chemistry Tokyo Institute of Technology, Tokyo 152-8551 Japan Department of Photo-Optical Engineering Tokyo Institute of Polytechnics Kanagawa 243-0297 Japan

Cite This Article

Michihisa Kawano, Tomokatsu Sano, Jiro Abe, et al. (1999). The First in Situ Direct Observation of the Light-Induced Radical Pair from a Hexaarylbiimidazolyl Derivative by X-ray Crystallography. Journal of the American Chemical Society, 121(35), 8106-8107. https://doi.org/10.1021/ja9903173

The First in Situ Direct Observation of the Light-Induced Radical Pair from a Hexaarylbiimidazolyl Derivative by X-ray Crystallography

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