TY - JOUR

T1 - Tuning the optical properties of the metal-organic framework UiO-66 via ligand functionalization

AU - Treger, Marvin

AU - Hannebauer, Adrian

AU - Schaate, Andreas

AU - Budde, Jan L.

AU - Behrens, Peter

AU - Schneider, Andreas M.

N1 - Funding Information: We acknowledge the support of the cluster system team at the Leibniz University of Hannover, Germany in the production of this work. This work is funded by the DFG under Germany's Excellence Strategy within the Cluster of Excellence PhoenixD (EXC 2122, Project ID 390833453). A. H. is grateful for being funded by the Hannover School for Nanotechnology (HSN) at the Laboratory of Nano and Quantum Engineering (LNQE). The HSN is funded by the Ministry of Science and Culture of Lower Saxony.

PY - 2023/2/3

Y1 - 2023/2/3

N2 - Metal-organic frameworks (MOFs) are a promising class of materials for optical applications, especially due to their modular design which allows fine-tuning of the relevant properties. The present theoretical study examines the Zr-based UiO-66-MOF and derivatives of it with respect to their optical properties. Starting from the well-known monofunctional amino- and nitro-functionalized UiO-66 derivatives, we introduce novel UiO-66-type MOFs containing bifunctional push-pull 1,4-benzenedicarboxylate (bdc) linkers. The successful synthesis of such a novel UiO-66 derivative is also reported. It was carried out using a para-nitroaniline (PNA)-based bdc-analogue linker. Applying density functional theory (DFT), suitable models for all UiO-66-MOF analogues were generated by assessing different exchange-correlation functionals. Afterwards, HSE06 hybrid functional calculations were performed to obtain the electronic structures and optical properties. The detailed HSE06 electronic structure calculations were validated with UV-Vis measurements to ensure reliable results. Finally, the refractive index dispersion of the seven UiO-66-type materials is compared, showing the possibility to tailor the optical properties by the use of functionalized linker molecules. Specifically, the refractive index can be varied over a wide range from 1.37 to 1.78.

AB - Metal-organic frameworks (MOFs) are a promising class of materials for optical applications, especially due to their modular design which allows fine-tuning of the relevant properties. The present theoretical study examines the Zr-based UiO-66-MOF and derivatives of it with respect to their optical properties. Starting from the well-known monofunctional amino- and nitro-functionalized UiO-66 derivatives, we introduce novel UiO-66-type MOFs containing bifunctional push-pull 1,4-benzenedicarboxylate (bdc) linkers. The successful synthesis of such a novel UiO-66 derivative is also reported. It was carried out using a para-nitroaniline (PNA)-based bdc-analogue linker. Applying density functional theory (DFT), suitable models for all UiO-66-MOF analogues were generated by assessing different exchange-correlation functionals. Afterwards, HSE06 hybrid functional calculations were performed to obtain the electronic structures and optical properties. The detailed HSE06 electronic structure calculations were validated with UV-Vis measurements to ensure reliable results. Finally, the refractive index dispersion of the seven UiO-66-type materials is compared, showing the possibility to tailor the optical properties by the use of functionalized linker molecules. Specifically, the refractive index can be varied over a wide range from 1.37 to 1.78.

UR - http://www.scopus.com/inward/record.url?scp=85148668055&partnerID=8YFLogxK

U2 - 10.1039/d2cp03746g

DO - 10.1039/d2cp03746g

M3 - Article

C2 - 36779311

AN - SCOPUS:85148668055

VL - 25

SP - 6333

EP - 6341

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 8

ER -