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Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal-Organic Frameworks

Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal-Organic Frameworks
Son, Ho-JinJin, ShengyePatwardhan, SameerWezenberg, Sander J.Jeong, Nak CheonSo, MonicaWilmer, Christopher E.Sarjeant, Amy A.Schatz, George C.Snurr, Randall Q.Farha, Omar K.Wiederrecht, Gary P.Hupp, Joseph T.
DGIST Authors
Jeong, Nak Cheon
Issued Date
Article Type
[5,15 Bis[4 (Pyridyl)Ethynyl] 10,20 Diphenylporphinato]Zinc (ii)[5,15 Dipyridyl 10,20 Bis(Pentafluorophenyl)Porphinato]Zinc (ii)AbsorptionAbsorption IntensityAcetyleneAcetylene DerivativeAddition ReactionAnisotropyAntennaCalculationChlorophyllConjugationControlled StudyCrystalline MaterialsEnergy-TransportEnergy ConversionEnergy MigrationEnergy TransferEthynylExciton MigrationExcitonsFluorescenceFluorescence QuenchingHarvestingHigh AnisotropyJava Programming LanguageLightLight-HarvestingLight-Harvesting SystemMetal Organic FrameworkMetalloporphyrinsMolecular StructureOrganometallic CompoundsPentafluorophenylPhotogenerated ExcitonsPhotosynthesisPorphyrinPorphyrin MoleculesPorphyrinsPyridylRelated CompoundsSolar EnergyStrutsTheoretical CalculationsTheoretical ModelUltra-FastUltra-Fast Energy MigrationUnclassified DrugZincZinc Compounds
Given that energy (exciton) migration in natural photosynthesis primarily occurs in highly ordered porphyrin-like pigments (chlorophylls), equally highly ordered porphyrin-based metal-organic frameworks (MOFs) might be expected to exhibit similar behavior, thereby facilitating antenna-like light-harvesting and positioning such materials for use in solar energy conversion schemes. Herein, we report the first example of directional, long-distance energy migration within a MOF. Two MOFs, namely F-MOF and DA-MOF that are composed of two Zn(II) porphyrin struts [5,15-dipyridyl-10,20-bis(pentafluorophenyl)porphinato]zinc(II) and [5,15-bis[4-(pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II), respectively, were investigated. From fluorescence quenching experiments and theoretical calculations, we find that the photogenerated exciton migrates over a net distance of up to ∼45 porphyrin struts within its lifetime in DA-MOF (but only ∼3 in F-MOF), with a high anisotropy along a specific direction. The remarkably efficient exciton migration in DA-MOF is attributed to enhanced π-conjugation through the addition of two acetylene moieties in the porphyrin molecule, which leads to greater Q-band absorption intensity and much faster exciton-hopping (energy transfer between adjacent porphyrin struts). The long distance and directional energy migration in DA-MOF suggests promising applications of this compound or related compounds in solar energy conversion schemes as an efficient light-harvesting and energy-transport component. © 2012 American Chemical Society.
American Chemical Society
Related Researcher
  • 정낙천 Jeong, Nak Cheon 화학물리학과
  • Research Interests Inorganic Chemistry; Metal-Organic Framework; Nanoporous Materials; Electron Transport;Ion Transport
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Department of Physics and Chemistry Supramolecular Inorganic Chemistry Laboratory 1. Journal Articles


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