Nonlinear Metal–Organic Framework Crystals for Efficient Multicolor Coherent Optical Emission

Abstract

Non‐centrosymmetric metal–organic frameworks (MOFs) have recently emerged as a promising class of coordination polymers for nonlinear optics and light conversion. Nevertheless, achieving high endurance and efficiency for the light conversion within the whole visible range by a single crystal of MOF remains a challenge. This article reports on the design of two non‐centrosymmetric MOFs based on a 1,3,5‐benzenetricarboxylic acid ligand and Er/Co ions, providing an efficient and simultaneous multiple second and third optical harmonic generations (SHG, THG) from 400 to 750 nm with a high endurance (over 100 cycles or 3 h of continuous operation). Optical experiments and quantum chemical modeling of the MOF single crystals confirm the polarization and chemistry‐dependent efficiency of SHG and THG, associated with the varied MOFs' symmetry and dipole moment. The observed coherent light conversion within the whole visible range by MOF single crystals at ambient conditions makes it possible to achieve the multicolor (up to three) coherent emission required for modern laser technologies, making MOFs highly competitive and sustainable materials for nonlinear optics.

From grayscale towards multi-color laser printing inside non-linear metal-organic framework microcrystals

“…As a model MOF we synthesized the previously reported Er-BTC [1,2], which consists of Er-ions and 1,3,5benzenetricarboxylic acid (Н3BTC) ligand and crystalizes in tetragonal P4122 space group. The optical transparency window of Er-BTC covers the entire visible range except several narrow absorption peaks at 450, 480, 515, and 650 nm associated with Er-ion centers.…”

Two chiral lanthanide PrIII and HoIII complexes: NIR luminescence and nonlinear optical properties

“…Ln III complexes usually exhibit satisfactory luminescence and magnetic properties stemming from the unique f -electron configurations of the Ln III ions, which have been extensively exploited. 46–52 In contrast, the known Ln III complexes with SHG and THG responses are unexpectedly insufficient, 53–62 especially for NIR-luminescent Ln III counterparts. 24,25 As far as we know, there is no report on Pr III and Ho III complexes displaying NIR luminescence properties and presenting SHG and THG responses simultaneously.…”

Application of DUT-4 MOF structure switching for optical and electrical humidity sensing

“…Transport of mass, heat, and optical properties in MOF structures, at least as important, is still an underexplored topic. 24–26 For practical applications, materials incorporating metal–organic frameworks based on carboxylate glass matrices are already being developed. 27,28 In particular, the influence of water on the process of synthesis of such compounds has been studied.…”