• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.19-31
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• 2005

During the last decade, the exploration of nanoscale device and circuitry based on molecules has gained increasing interest. In parallel with this, considerable effort is being devoted to the development of molecular photonic/electronic materials based on various porphyrin arrays. This involves light as an input/output signal and excitation energy migration as a mechanism for signal transmission. Absorption of a photon at the light collector end of the porphyrin array yields the excited state, which migrates among the intervening pigments until reaching the emitter, whereupon another photon is emitted. As a consequence, it is relevant to understand the excitation energy transfer (EET) processes occurring in various forms of porphyrin arrays for the applications as artificial light harvesting arrays and molecular photonic/electronic wires. Since the excitonic (dipole) and electronic (conjugation) couplings between the adjacent porphyrin moieties in porphyrin arrays govern the EET processes, we have characterized the EET rates of various forms of multiporphyrin arrays (linear, cyclic, and box) based on various time-resolved spectroscopic measurements. We believe that our observations provide a platform for further development of molecular photonic/electronic materials based on porphyrin arrays.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.271-276
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• 2002

The energy relaxation dynamics of the lowest excited singlet and triplet states of the Zn(II)porphyrin monomer and its directly linked arrays were comparatively investigated with increasing the number of porphyrin moieties. While the fluorescence decay rates and quantum yields of the porphyrin arrays increased with the increase of porphyrin units, their triplet-triplet (T-T) absorption spectra and decay times remained almost the same. The difference in the trends of energy relaxation dynamics between the excited singlet and triplet states has been discussed in view of the electronic orbital configurations.

• Proceeding of EDISON Challenge
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• 2015.03a
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• pp.163-166
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• 2015

Intramolecular energy migration in a cyclic porphyrin array is spontaneous transfer of energy from one excited site to another. Since the efficiency of energy migration is inversely proportional to distance, the energy migration is occurred on their adjacent sites more often than distant ones. Therefore, the energy migration in the cyclic porphyrin array is largely dependent on their conformational characters. However, evaluation of conformational information by means of experimental tools is ambiguous since their limited resolution. In this work, we calculate the internal angle and distance distributions of cyclic porphyrin arrays using molecular dynamics simulations to obtain conformational information. To evaluate the angle and distance distributions respect to molecular size, we constructed molecules with n porphyrin dimers (n=1,3,7) in implicit solvent environment. Performing molecular dynamics simulations, we modulated alkyl groups to investigate additional conformational effects of the system.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.197-201
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• 2008

Conformational heterogeneity of directly linked multiporphyrin arrays with larger molecular length retards their utilities in practical applications such as two-photon absorption and molecular photonic wire. In this regard, here we adopted a way to overcome the conformational heterogeneity through hydrogen bonding by selective binding of meso aryl substituents of porphyrins (host) with urea (guest) to form helical structure. Using steady-state and time-resolved spectroscopy, we observed the enhanced fluorescence quantum yield by ~1.8 to 2.4 times, enhanced anisotropy values and the disappearance of fast fluorescence decay component in the host-guest helical forms. In addition, the enhanced nonlinear optical responses of helical arrays infer the extended inter-porphyrin electronic coupling due to a significant change in dihedral angle between the neighboring porphyrin moieties. The current host-guest strategy will provide a guideline to improve the structural homogeneity of the photonic wire.

• Bulletin of the Korean Chemical Society
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• v.26 no.10
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• pp.1505-1511
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• 2005

The excitation energy transfer process occurring in energy donor-acceptor linked porphyrin array system is theoretically simulated using the on-the-fly filtered propagator path integral method. The compound consists of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin, in which the donor array and the acceptor are linked via a 1,4-phenylene spacer. Real-time path integral simulations provide time-evolution of the site population and the excitation energy transfer rate constants are determined. Simulations and experiments show an excellent agreement indicating that the path integration is a useful tool to investigate the energy transfer dynamics in molecular assemblies.

• Proceedings of the Korean Society of Potoscience Conference
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• spring
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• pp.31-31
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• 1999

• Proceedings of the Korean Society of Potoscience Conference
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• 2005.06a
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• pp.133-133
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• 2005