Photophysics, Dynamics, and Energy Transfer in Rigid Mimics of GFP-based Systems.
Engineering of novel systems capable of efficient energy capture and transfer in a predesigned pathway could potentially boost applications varying from organic photovoltaics to catalytic platforms and have implications for energy sustainability and green chemistry. While light-harvesting properties of different materials have been studied for decades, recently, there has been great progress in the understanding and modeling of short- and long-range energy transfer processes through utilization of metal-organic frameworks (MOFs). In this Forum Article, the recent advances in efficient multiple-chromophore coupling in well-defined metal-organic materials through mimicking a protein system possessing near 100% energy transfer are discussed. Utilization of a MOF as an efficient replica of a protein β-barrel to maintain chromophore emission was also demonstrated. Furthermore, we established a novel dependence of a photophysical response on an electronic configuration for chromophores with the benzylidene imidazolinone core. For that, we prepared 16 chromophores, in which the benzylidene imidazolinone core was modified with electron-donating and electron-withdrawing substituents. To establish the structure-dependent photophysical properties of the prepared chromophores, 11 novel molecular structures were determined by single-crystal X-ray diffraction. These findings allow one to predict the chromophore emission profile inside a rigid framework as a function of the substituent, a key parameter for achieving the spectral overlap necessary to study and increase resonance energy transfer efficiency in MOF-based materials.
Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
Ekaterina A
EA
Dolgopolova
Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
Allison M
AM
Rice
Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
Mark D
MD
Smith
Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
Natalia B
NB
Shustova
D001593:Benzyl Compounds / Q000737:chemistry; D018360:Crystallography, X-Ray; D003573:Cytochrome b Group / Q000737:chemistry; D004735:Energy Transfer; D029968:Escherichia coli Proteins / Q000737:chemistry; D049452:Green Fluorescent Proteins / Q000737:chemistry; D048288:Imidazolines / Q000737:chemistry; D000073396:Metal-Organic Frameworks / Q000737:chemistry*
D001593:Benzyl Compounds; D003573:Cytochrome b Group; D029968:Escherichia coli Proteins; D048288:Imidazolines; D000073396:Metal-Organic Frameworks; D049452:Green Fluorescent Proteins; C017850:cytochrome b562, E coli