P. Van der Voort

N‐rich porous polymer with isolated Tb3+‐ions displays unique temperature dependent behavior through the absence of thermal quenching

F. Vanden Bussche, A.M. Kaczmarek, S. K. P. Veerapandian, J. Everaert, M. Debruyne, S. Abednatanzi, R. Morent, N. De Geyter, V. Van Speybroeck, P. Van der Voort, C.V. Stevens
Chemistry - A European Journal
26 (67), 15596-15604
2020
A1

Abstract 

The challenge of measuring fast moving or small scale samples is based on the absence of contact betw een sample and sensor. Grafting lanthanides onto hybrid materials arises as one of the most promising accurate techniques to obtain noninvasive thermometers. In this w ork, a novel bipyridine based Porous Organic Polymer (bpyDATPOP) wasinvestigatedastemperaturesensorafter grafting w ith Eu(acac) 3 and Tb(acac) 3 complexes. The bpyDAT POP successfully showed temperature dependent behavior in the 10 ‐ 310 K range, proving the potential of amorphous, porous organic framew orks. More intriguingly, w e observed unique temperature dependent behavior; instead of the standard observed change in emission as a result of a change in temperature for both Eu 3+ and Tb 3+ , the emission spectrumof Tb 3+ remained constant. This w ork provides framework‐ and energy‐based explanations for the observed phenomenon. The conjugation in the bpyDAT POP framew ork is interrupted, creating energetically isolated Tb 3+ environments. Energy transferfromTb 3+ toEu 3+ isthereforeabsent,norenergybacktransfer from Tb 3+ to bpyDAT POP ligand (i.e. no thermal quenching) is detected.

Open Access version available at UGent repository
Gold Open Access

DOI 

http://dx.doi.org/10.1002/chem.202002009

Elucidating the promotional effect of a covalent triazine framework in aerobic oxidation

S. Abednatanzi, P. Gohari Derakhshandeh, P. Tack, F. Muniz-Miranda, Y-Y Liu, J. Everaert, M. Meledina, F. Vanden Bussche, L. Vincze, C. Stevens, V. Van Speybroeck, H. Vrielinck, F. Callens, K. Leus, P. Van der Voort
Applied Catalysis B: Environmental
269, 118769
2020
A1

DOI 

http://dx.doi.org/10.1016/j.apcatb.2020.118769

Engineering a highly defective stable UiO-66 with tunable Lewis-Brønsted acidity - The role of the hemilabile linker

X. Feng, J. Hajek, H. S. Jena, G. Wang, S. K. P. Veerapandian, R. Morent, N. De Geyter, K. Leyssens, A.E.J. Hoffman, V. Meynen, C. Marquez, D. De Vos, V. Van Speybroeck, K. Leus, P. Van der Voort
JACS (Journal of the American Chemical Society)
142 (6), 3174-3183
2020
A1

Abstract 

The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to maximum 6 defects per cluster in UiO-66. We have synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects, but also as a co-ligand that enhances the stability of the resulting defective framework. Furthermore, upon a post-synthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (3 per formula unit), leaving the Zr-nodes on average 6-fold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of α-pinene oxide. This reaction is particularly sensitive to the Brønsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Brønsted acid sites, the Hl-UiO-66 and the post-synthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Brønsted to Lewis acid ratio in the materials, and thus their catalytic activity and selectivity.

DOI 

http://dx.doi.org/10.1021/jacs.9b13070

Optical Properties of Isolated and Covalent Organic Framework-Embedded Ruthenium Complexes

F. Muniz-Miranda, L. De Bruecker, A. De Vos, F. Vanden Bussche, C.V. Stevens, P. Van der Voort, K. Lejaeghere, V. Van Speybroeck
Journal of Physical Chemistry A
123 (32), 6854-6867
2019
A1

Abstract 

Heterogenization of RuL3 complexes on a support with proper anchor points provides a route toward design of green catalysts. In this paper, Ru(II) polypyridyl complexes are investigated with the aim to unravel the influence on the photocatalytic properties of varying nitrogen content in the ligands and of embedding the complex in a triazine-based covalent organic framework. To provide fundamental insight into the electronic mechanisms underlying this behavior, a computational study is performed. Both the ground and excited state properties of isolated and anchored ruthenium complexes are theoretically investigated by means of density functional theory and time-dependent density functional theory. Varying the ligands among 2,2′-bipyridine, 2,2′-bipyrimidine, and 2,2′-bipyrazine allows us to tune to a certain extent the optical gaps and the metal to ligand charge transfer excitations. Heterogenization of the complex within a CTF support has a significant effect on the nature and energy of the electronic transitions. The allowed transitions are significantly red-shifted toward the near IR region and involve transitions from states localized on the CTF toward ligands attached to the ruthenium. The study shows how variations in ligands and anchoring on proper supports allows us to increase the range of wavelengths that may be exploited for photocatalysis.

Gold Open Access

DOI 

http://dx.doi.org/10.1021/acs.jpca.9b05216

Electronic properties of heterogenized Ru(II) polypyridyl photoredox complexes on covalent triazine frameworks

A. De Vos, K. Lejaeghere, F. Muniz-Miranda, C. Stevens, P. Van der Voort, V. Van Speybroeck
Journal of Materials Chemistry A
7, 8433-8442
2019
A1

Abstract 

Ru(II) polypyridyl complexes have been successful for a wide range of photoredox applications thanks to their efficient light-induced metal-to-ligand charge transfer. Using the computational framework of density-functional theory, we report how these complexes can be anchored onto covalent triazine frameworks while maintaining their favorable electronic properties. We moreover show that variation of the nitrogen content of the framework linkers or complex ligands endows the heterogenized catalyst with a unique versatility, spanning a wide range of absorption characteristics and redox potentials. By judiciously choosing the catalyst building blocks, it is even possible to selectively guide the charge transfer toward either the scaffold or the accessible pore sites. Rational design of sustainable and efficient photocatalysts thus comes within reach.

DOI 

http://dx.doi.org/10.1039/C9TA00573K

Immobilization of Ir(I) complex on Covalent Triazine Frameworks for C-H Borylation Reactions: A Combined Experimental and Computational Study

N. Tahir, F. Muniz-Miranda, J. Everaert, P. Tack, T.S.A Heugebaert, K. Leus, L. Vincze, C. Stevens, V. Van Speybroeck, P. Van der Voort
Journal of Catalysis
371, 135-143
2019
A1

Abstract 

Metal-modified covalent triazine frameworks (CTFs) have attracted considerable attention in heterogeneous catalysis due to their strong nitrogen-metal interactions exhibiting superior activity, stability and hence recyclability. Herein, we report on a post-metalation of a bipyridine-based CTFs with an Ir(I) complex for CH borylation of aromatic compounds. Physical characterization of the Ir(I)-based bipyCTF catalyst in combination with density functional theory (DFT) calculations exhibit a high stabilization energy of the Ir-bipy moiety in the frameworks in the presence of B2Pin2. By using B2Pin2 as a boron source, Ir(I)@bipyCTF efficiently catalyzed the CH borylation of various aromatic compounds with excellent activity and good recyclability. In addition, XAS analysis of the Ir(I)@bipyCTF gave clear evidence for the coordination environment of the Ir.

DOI 

http://dx.doi.org/10.1016/j.jcat.2019.01.030

Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach

A.E.J. Hoffman, L. Vanduyfhuys, I. Nevjestic, J. Wieme, S.M.J. Rogge, H. Depauw, P. Van der Voort, H. Vrielinck, V. Van Speybroeck
Journal of Physical Chemistry C
122, 5, 2734-2746
2018
A1

Abstract 

In this work mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed allowing for the identification of all IR active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable to determine the theoretical Raman spectrum of the closed- and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed- and large-pore phases indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.

Open Access version available at UGent repository
Gold Open Access

DOI 

http://dx.doi.org/10.1021/acs.jpcc.7b11031

A series of sulfonic acid functionalized mixed-linker DUT-4 analogues: synthesis, gas sorption properties and catalytic performance

G. Wang, K. Leus, K. Hendrickx, J. Wieme, H. Depauw, Y-Y Liu, V. Van Speybroeck, P. Van der Voort
Dalton Transactions
46, 14356
2017
A1

Abstract 

In this work, we present the successful synthesis of a series of sulfonic acid functionalized mixed-linker metal–organic frameworks (MOFs) having the DUT-4 topology by using different ratios of 2,6-naphthalenedicarboxylic acid (H2-NDC) and 4,8-disulfonaphthalene-2,6-dicarboxylic acid (H2-NDC-2SO3H) in one-pot reactions. The obtained materials were fully characterized and their CO2 adsorption properties at low and high pressures were studied and compared with those of the pristine DUT-4 material. Generally, the CO2 adsorption capacities range from 3.28 and 1.36 mmol g−1 for DUT-4 to 1.54 and 0.78 mmol g−1 for DUT-4-SO3H (50) up to 1 bar at 273 K and 303 K, respectively. Computational calculations corroborated the structural changes of the material in function of the loading of sulfonic acid groups. Furthermore, due to the strong Brønsted acid character, the resulting sulfonic acid based MOF material was evaluated as a catalyst for the ring opening of styrene oxide with methanol as a nucleophile under mild conditions, showing almost full conversion (99%) after 5 hours of reaction. A hot filtration experiment demonstrated that the catalysis occurred heterogeneously and the catalyst could be recovered and reused for multiple runs without significant loss in activity and crystallinity.

DOI 

http://dx.doi.org/10.1039/C7DT02752D

Missing linkers: an alternative pathway to UiO-66 electronic structure engineering

A. De Vos, K. Hendrickx, P. Van der Voort, V. Van Speybroeck, K. Lejaeghere
Chemistry of Materials
29 (7), 3006–3019
2017
A1

Abstract 

UiO-66 is a promising metal-organic framework for photocatalytic applications. However, the ligand-to-metal charge transfer of an excited electron is inefficient in the pristine material. Herein we assess the influence of missing linker defects on the electronic structure of UiO-66 and discuss their ability to improve ligand-to-metal charge transfer. Using a new defect classification system, which is transparent and easily extendable, we identify the most promising photocatalysts by considering both relative stability and electronic structure. We find the properties of UiO-66 defect structures largely to depend on the coordination of the constituent nodes, and the nodes with the strongest local distortions to alter the electronic structure most. Defects hence provide an alternative pathway to tune UiO-66 for photocatalytic purposes, besides linker modification and node metal substitution. In addition, the decomposition of MOF properties into node- and linker-based behavior is more generally valid, so we propose orthogonal electronic structure tuning as a paradigm in MOF electronic structure engineering.

Open Access version available at UGent repository
Gold Open Access

DOI 

http://dx.doi.org/10.1021/acs.chemmater.6b05444

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