| Autor: |
Martin CR; Savannah River National Laboratory, Aiken, South Carolina 29808, United States., Thaggard GC; Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States., Lehman-Andino I; Savannah River National Laboratory, Aiken, South Carolina 29808, United States., Mollinedo E; Savannah River National Laboratory, Aiken, South Carolina 29808, United States., Rai BK; Savannah River National Laboratory, Aiken, South Carolina 29808, United States., Page MA; Savannah River National Laboratory, Aiken, South Carolina 29808, United States., Taylor-Pashow K; Savannah River National Laboratory, Aiken, South Carolina 29808, United States., Shustova NB; Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States. |
| Abstrakt: |
Optoelectronic devices based on lanthanide-containing materials are an emergent area of research due to imminent interest in a new generation of diode materials, optical and magnetic sensors, and ratiometric thermometers. Tailoring material properties through the employment of photo- or thermochromic moieties is a powerful approach that requires a deep fundamental understanding of possible cooperativity between lanthanide-based metal centers and integrated switchable units. In this work, we probe this concept through the synthesis, structural analysis, and spectroscopic characterization of novel photochromic lanthanide-based metal-organic materials containing noncoordinatively integrated photoresponsive 4,4'-azopyridine between lanthanide-based metal centers. As a result, a photophysical material response tailored on demand through the incorporation of photochromic compounds within a rigid matrix was investigated. The comprehensive analysis of photoresponsive metal-organic materials includes single-crystal X-ray diffraction and diffuse reflectance spectroscopic studies that provide guiding principles necessary for understanding photochromic unit-lanthanide-based metal-organic framework (MOF) cooperativity. Furthermore, steady-state and time-resolved diffuse reflectance spectroscopic studies revealed a rapid rate of photoresponsive moiety attenuation upon its integration within the rigid matrix of lanthanide-based MOFs in comparison with that in solution, highlighting a unique role and synergy that occurred between stimuli-responsive moieties and the lanthanide-based MOF platform, allowing for tunability and control of material photoisomerization kinetics. |
