Direct laser writing (DLW) is an industry-oriented method for creating the images both on the surface and in the volume of various media for nanophotonic, medicine, bioengineering, and even IT applications. However, the challenges on the creation of color images with sub-diffraction resolution inside the media, as well as the impossibility of achieving black and grayscale shades simultaneously with full color palette significantly hinder the widespread use of DLW. Staying in the laser writing paradigm, we have proposed a new concept for simultaneous multicolor and grayscale writing inside the media with sub-diffraction resolution through the use of a whole class of non-linear optical (NLO) metal-organic frameworks (MOFs).
The integration of metal-organic frameworks (MOFs) as coordination polymers into the field of nonlinear optics and light conversion has recently attracted significant attention. However, the challenge of achieving high endurance and efficiency for light conversion throughout the entire visible range using a single MOF crystal persists. In this work, we present the design of a non-centrosymmetric MOF based on a 1,3,5-benzenetricarboxylic acid ligand and Erbium (Er) ions, which demonstrates efficient and simultaneous generation of multiple second and third optical harmonics (SHG, THG) across a wavelength range of 400 to 750 nm. Through a combination of optical experiments we have confirmed the effectiveness of SHG and THG in the MOF single crystals. These phenomena are caused by the specific MOF space group and the associated dipole moment. The observation of coherent light conversion throughout the entire visible range by MOF single crystals under ambient conditions enables the realization of multicolor (up to 3) emission, which is essential for modern laser technologies.
An approach to the study of the porous structure of metal-organic frameworks (MOF) using guest luminescent molecules with specially selected spectral characteristics as acceptors of electronic excitation energy was suggested. If such molecules are adsorbed in MOF pores with sizes comparable to the Förster radius, Förster resonance energy transfer (FRET) from photoexcited linkers occurs. In this case quenching of luminescence of the linker can serve as analytical signals indicating open pore structure of the MOF. The developed approach was demonstrated by the example of DUT-8(Zn) MOF and Coumarin 1 as guest molecules by time-resolved luminescence methods.
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