Supramolecular structures and photoelectronic properties of the inclusion complex of a cyclic free-base porphyrin dimer and C60

Hirofumi Nobukuni, Yuichi Shimazaki, Hidemitsu Uno, Yoshinori Naruta, Kei Ohkubo, Takahiko Kojima, Shunichi Fukuzumi, Shu Seki, Hayato Sakai, Taku Hasobe, Fumito Tani

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Abstract

A cyclic free-base porphyrin dimer H4-CPDPy (CPD = cyclic porphyrin dimer) linked by butadiyne moieties bearing 4-pyridyl groups self-assembles to form a novel porphyrin nanotube in the crystalline state. The cyclic molecules link together through nonclassical C-H···N hydrogen bonds and π-π interactions of the pyridyl groups along the crystallographic a axis. H4-CPDPy includes a C 60 molecule in its cavity in solution. In the crystal structure of the inclusion complex (C60⊂H4-CPDPy), the dimer "bites" a C60 molecule by tilting the porphyrin rings with respect to each other, and there are strong π-π interactions between the porphyrin rings and C60. The included C60 molecules form a zigzag chain along the crystallographic b axis through van der Waals contacts with each other. Femtosecond laser flash photolysis of C 60⊂H4-CPDPy in the solid state with photoexcitation at 420 nm shows the formation of a completely charge-separated state {H4-CPDPy•+ + C60 •-}, which decays with a lifetime of 470 ps to the ground state. The charge-carrier mobility of the single crystal of C60⊂H 4-CPDPy was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. C60cH 4-CPDPy has an anisotropic charge mobility (σμ = 0.16 and 0.13cm 2V-1s-1) along the zigzag chain of C60 (which runs at 45° and parallel to the crystallographic b axis). To construct a photoelectrochemical cell, C60⊂H 4-CPDPy was deposited onto nanostructured SnO2 films on a transparent electrode. The solar cell exhibited photovoltaic activity with an incident photon to current conversion efficiency of 17 %.

Original languageEnglish
Pages (from-to)11611-11623
Number of pages13
JournalChemistry - A European Journal
Volume16
Issue number38
DOIs
Publication statusPublished - 2010 Oct 11

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Porphyrins
Dimers
Molecules
Photolysis
Bearings (structural)
Photoelectrochemical cells
Photoexcitation
Carrier mobility
Ultrashort pulses
Charge carriers
Nanotubes
Ground state
Conversion efficiency
Solar cells
Hydrogen bonds
Photons
Crystal structure
Microwaves
Single crystals
Crystalline materials

Keywords

  • Charge transfer
  • Fullerenes
  • Photoinduced electron transfer
  • Photovoltaics
  • Porphyrinoids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Supramolecular structures and photoelectronic properties of the inclusion complex of a cyclic free-base porphyrin dimer and C60. / Nobukuni, Hirofumi; Shimazaki, Yuichi; Uno, Hidemitsu; Naruta, Yoshinori; Ohkubo, Kei; Kojima, Takahiko; Fukuzumi, Shunichi; Seki, Shu; Sakai, Hayato; Hasobe, Taku; Tani, Fumito.

In: Chemistry - A European Journal, Vol. 16, No. 38, 11.10.2010, p. 11611-11623.

Research output: Contribution to journalArticle

Nobukuni, H, Shimazaki, Y, Uno, H, Naruta, Y, Ohkubo, K, Kojima, T, Fukuzumi, S, Seki, S, Sakai, H, Hasobe, T & Tani, F 2010, 'Supramolecular structures and photoelectronic properties of the inclusion complex of a cyclic free-base porphyrin dimer and C60', Chemistry - A European Journal, vol. 16, no. 38, pp. 11611-11623. https://doi.org/10.1002/chem.201001815
Nobukuni, Hirofumi ; Shimazaki, Yuichi ; Uno, Hidemitsu ; Naruta, Yoshinori ; Ohkubo, Kei ; Kojima, Takahiko ; Fukuzumi, Shunichi ; Seki, Shu ; Sakai, Hayato ; Hasobe, Taku ; Tani, Fumito. / Supramolecular structures and photoelectronic properties of the inclusion complex of a cyclic free-base porphyrin dimer and C60. In: Chemistry - A European Journal. 2010 ; Vol. 16, No. 38. pp. 11611-11623.
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