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Temperature-dependent interchromophoric interaction in a fluorescent pyrene-based metal-organic framework.

ABSTRACT: Compounds exhibiting tuneable fluorescence emission upon heating or cooling are considered smart materials as their optical properties can be exquisitely controlled by adjusting the external temperature. Herein, we report such a material, which is a porous pyrene-based metal-organic framework with a chemical formula of [Mg_1.5(HTBAPy)(H₂O)₂]·3DMF (H₄TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene), named SION-7. The bulk solid material of SION-7 can display either monomer or excimer fluorescence emission due to the temperature-dependent extent of interchromophoric interactions between the HTBAPy^3- ligands within the framework. Consequently, the fluorescence emission colours gradually change from blue at low temperature (80 K) to yellow-green at high temperature (450 K). Interestingly, while kept in a relatively wide temperature range of 80-200 K, SION-7 displays a structured monomer-like spectrum and its colour changes reversibly from deep to light blue. Ex situ variable-temperature (100-350 K) single-crystal X-ray diffractometry studies revealed the impact of solvent content on the optical properties of SION-7, and illustrated the correlation between the position of the phenylene groups of the HTBAPy^3- ligands at different temperatures and the interchromophoric interaction. Our study demonstrates a step forward towards the design of tuneable thermofluorochromic materials sought by optoelectronics.

SUBMITTER: Gladysiak A

PROVIDER: S-EPMC6585595 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Temperature-dependent interchromophoric interaction in a fluorescent pyrene-based metal-organic framework.

Gładysiak Andrzej A Nguyen Tu N TN Bounds Richard R Zacharia Anna A Itskos Grigorios G Reimer Jeffrey A JA Stylianou Kyriakos C KC

Chemical science 20190514 24

Compounds exhibiting tuneable fluorescence emission upon heating or cooling are considered smart materials as their optical properties can be exquisitely controlled by adjusting the external temperature. Herein, we report such a material, which is a porous pyrene-based metal-organic framework with a chemical formula of [Mg1.5(HTBAPy)(H2O)2]·3DMF (H4TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene), named SION-7. The bulk solid material of < ...[more]

PMID: 31360420

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Project description:Solvent-assisted ligand incorporation (SALI) of the ditopic linker 5-carboxy-3-(4-carboxybenzyl)thiazolium bromide [(H2PhTz)Br] into the zirconium metal-organic framework NU-1000 [Zr6O4(OH)8(H2O)4(TBAPy)2, where NU = Northwestern University and H4TBAPy = 1,3,6,8-tetrakis(p-benzoic-acid)pyrene], led to the SALIed NU-1000-PhTz material of minimal formula [Zr6O4(OH)6(H2O)2(TBAPy)2(PhTz)]Br. NU-1000-PhTz has been thoroughly characterized in the solid state. As confirmed by powder X-ray diffraction, this material keeps the same three-dimensional architecture of NU-1000 and the dicarboxylic extra linker bridges adjacent [Zr6] nodes ca. 8 Å far apart along the crystallographic c-axis. The functionalized MOF has a BET specific surface area of 1560 m2/g, and it is featured by a slightly higher thermal stability than its parent material (Tdec = 820 vs. 800 K, respectively). NU-1000-PhTz has been exploited for the capture and separation of two pollutant gases: carbon dioxide (CO2) and nitrous oxide (N2O). The high thermodynamic affinity for both gases [isosteric heat of adsorption (Qst) = 25 and 27 kJ mol-1 for CO2 and N2O, respectively] reasonably stems from the strong interactions between these (polar) "stick-like" molecules and the ionic framework. Intriguingly, NU-1000-PhTz shows an unprecedented temperature-dependent adsorption capacity, loading more N2O in the 298 K ≤ T ≤ 313 K range but more CO2 at temperatures falling out of this range. Grand canonical Monte Carlo simulations of the adsorption isotherms confirmed that the preferential adsorption sites of both gases are the triangular channels (micropores) in close proximity to the polar pillar. While CO2 interacts with the thiazolium ring in an "end-on" fashion through its O atoms, N2O adopts a "side-on" configuration through its three atoms simultaneously. These findings open new horizons in the discovery of functional materials that may discriminate between polluting gases through selective adsorption at different temperatures.

Dataset Information

Temperature-dependent interchromophoric interaction in a fluorescent pyrene-based metal-organic framework.

Publications

Temperature-dependent interchromophoric interaction in a fluorescent pyrene-based metal-organic framework.

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