Localized orbital study on the electronic structure of phthalocyanine dimers

Ishikawa, Naoto; Ohno, Osamu; Kaizu, Youkoh; Kobayashi, Hiroshi

doi:10.1021/j100201a028

Cited by 110 publications

(111 citation statements)

References 14 publications

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“…12,13 The close proximity of the two rings (2.8 Å for lutetium) gives rise to delocalized charge distributions and results in strong CT coupling due to significant wavefunction overlap. 14 The resulting high degree of charge carrier mobility readily explains their semiconductivity 15,16 and electrochromic behavior. 17,18 In its electronic ground state, lutetium bisphthalocyanine ([LuPc 2 ]) is a stable radical ([LuPc 2 ]…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, the anion ([LuPc 2 ] − ) exhibits CT states in the same energy range as the LE states. 14 The additional CT coupling drastically changes the electronic structure and gives rise to two bands in the linear absorption spectrum (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…14 The presence of an environmental asymmetry breaks the energetic degeneracy of the CT states, lowering the energy of the CT state on one side of the complex and enables a net transfer of charge after photo-excitation. In the RC, such asymmetry arises from differences in the electronic couplings among pigments due to slightly different spacings between the cofactor units, 20 distinct dielectric environments due to intra-protein electric fields, [21][22][23] and different hydrogen bonding pattern around the central units.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast photo-induced charge transfer unveiled by two-dimensional electronic spectroscopy

Bixner

Lukeš

Mančal

et al. 2012

The Journal of Chemical Physics

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The interaction of exciton and charge transfer (CT) states plays a central role in photo-induced CT processes in chemistry, biology, and physics. In this work, we use a combination of two-dimensional electronic spectroscopy (2D-ES), pump-probe measurements, and quantum chemistry to investigate the ultrafast CT dynamics in a lutetium bisphthalocyanine dimer in different oxidation states. It is found that in the anionic form, the combination of strong CT-exciton interaction and electronic asymmetry induced by a counter-ion enables CT between the two macrocycles of the complex on a 30 fs timescale. Following optical excitation, a chain of electron and hole transfer steps gives rise to characteristic cross-peak dynamics in the electronic 2D spectra, and we monitor how the excited state charge density ultimately localizes on the macrocycle closest to the counter-ion within 100 fs. A comparison with the dynamics in the radical species further elucidates how CT states modulate the electronic structure and tune fs-reaction dynamics. Our experiments demonstrate the unique capability of 2D-ES in combination with other methods to decipher ultrafast CT dynamics.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ultrafast photo-induced charge transfer unveiled by two-dimensional electronic spectroscopy

Bixner

Lukeš

Mančal

et al. 2012

The Journal of Chemical Physics

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“…The amplitude of cp2 rises on a 30 fs timescale, while the amplitude of cp1 shows a delayed rise. Neither the double peak structure of the low energy band nor the distinct cross-peak dynamics are predicted by the exciton model previously used to describe [LuPc 2 ]  [3]. To find the origin of these additional transitions, we investigated the influence of the counter-ion on the electronic structure by TD-DFT calculations [4].…”

Section: Resultsmentioning

confidence: 99%

“…In the neutral form, the single transition in the linear absorption spectrum can be understood as a transition to the upper state in an H-type dimer formed by resonance coupling between the LEs on each of the rings. For the anion, configuration interaction between inter-ring CTand LE-states yields a double peak structure in the linear absorption spectrum [3]. For a symmetric complex, each transition is two-(anion) or four-fold (radical) degenerate.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Charge Transfer Visualized by Two-Dimensional Electronic Spectroscopy

Bixner

Christensson

Hauer

et al. 2013

EPJ Web of Conferences

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Abstract. Two-dimensional electronic spectroscopy (2D-ES) is used to investigate ultrafast excited-state dynamics in a lutetium bisphthalocyanine dimer. Following optical excitation, a chain of electron and hole transfer steps gives rise to characteristic cross-peak dynamics in the electronic 2D spectra. The combination of density matrix propagation and quantum chemical calculations results in a molecular view of the charge transfer dynamics and highlights the role of the counter-ion in providing an energetic perturbation which promotes charge transfer across the complex.

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Axially Polarized NIR Absorption Bands in Electron-deficient Lanthanide Phthalocyanine Dimers and Trimers

Ishikawa

Kaizu

1999

J. Porphyrins Phthalocyanines

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Absorption and MCD spectra of the two-electron oxidized lutetium phthalocyanine trimer [( Pc ) Lu ( CRPc ) Lu ( Pc )]2+ ( Pc ≡ phthalocyanine ; CRPc ≡ 15- crown -5- substituted Pc ) as well as the MCD spectrum of the oxidized lutetium Pc dimer [ Lu ( Pc )2]+ are reported. These ‘two-electron-deficient’ Pc stacks show absorption bands in the NIR region whose intensities are comparable with those of the Q bands. The band of [ Lu ( Pc )2]+ showed only an MCD B term with no A term contribution, from which we assign the band to a non-degenerate transition whose transition moments are perpendicular to the Pc planes. In both trimer and dimer cases the excitation energy is higher than that of the corresponding NIR band in the ‘one-electron-deficient’ Pc stack [( Pc ) Lu ( CRPc ) Lu ( Pc )]+ or [ Lu ( Pc )2], but the magnitudes of the shift were significantly different (1500 cm−1 in the trimer and 4500 cm−1 in the dimer). The energy shifts are shown to be represented by a pair of two-electron repulsion integrals in a localized orbital basis. The model reproduced well the direction and magnitude of the shifts using numerical values of the integrals.

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Localized orbital study on the electronic structure of phthalocyanine dimers

Cited by 110 publications

References 14 publications

Ultrafast photo-induced charge transfer unveiled by two-dimensional electronic spectroscopy

Ultrafast photo-induced charge transfer unveiled by two-dimensional electronic spectroscopy

Ultrafast Charge Transfer Visualized by Two-Dimensional Electronic Spectroscopy

Axially Polarized NIR Absorption Bands in Electron-deficient Lanthanide Phthalocyanine Dimers and Trimers

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