Center for Molecular Modeling - L. De Bruecker

On the Prediction of Spectroscopic Fingerprints of Co2+ Complexes Relevant for the ZIF Nucleation Process

leen — Mon, 02 Oct 2023 07:58:28 +0000

L. De Bruecker, M. Filez, V. Van Speybroeck

Inorganic Chemistry

Volume: 62, Issue: 40, Pages: 16304-16322

2023

Abstract

The nucleation process of zeolitic imidazolate frameworks (ZIFs) is to date not completely understood. Recently, it has been found that, during the formation of Co-ZIF-67, after mixing imidazole-type ligands with octahedral precursors containing oxygen-coordinated ligands, a metal–organic pool with a diversity of transition metal complexes (TMCs) is formed showing fingerprints of octahedral and tetrahedral Co²⁺ complexes with both types of ligands [Filez, M. Cell Rep. Phys. Sci. 2021, 2, 100680]. In order to further unravel this process, we aim to characterize the d–d transitions of the TMCs and focus on their number, intensity, and position, which change during the process and can thus serve as a fingerprint for the formed species. It was previously shown that the number of ligands and symmetry has a detrimental influence on the ground state properties of Co²⁺ TMCs. Herein, we investigate how far excited state properties of TMCs relevant during nanoporous formation processes can be predicted by time-dependent density functional theory (TDDFT) and ligand field density functional theory (LFDFT). As TMCs are known to be challenging systems with possibly degenerate ground states and double excitations, we first investigate the performance of both techniques on first-row octahedral aqua-complexes. With this knowledge, we then focus on tetrahedral Co²⁺ complexes with aqua and imidazole-type ligands in order to investigate in how far we can propose a spectroscopic fingerprint that allows us to follow the Co²⁺ complexes during the formation of Co-ZIF-67. The results of TDDFT and LFDFT are qualitatively in agreement and provide complementary information. We found that various features can be used to distinguish between the species. However, as LFDFT is not suited for TMCs possessing the extended imidazole-type ligands and double and spin-flip states are not included in TDDFT, both techniques need to be complemented with more advanced methods to obtain complete insight into the d–d excitations of TMCs with imidazole ligands. Therefore, we particularly explored ab initio ligand field theory, which is capable of describing double excitations and is, in contrast to LFDFT, suitable for TMCs with extended ligands.

DOI

http://dx.doi.org/10.1021/acs.inorgchem.3c01355

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acs.inorgchem.3c01355.pdf

Influence of the number of ligands and point group on the electronic structure of Co2+ aqua-complexes

liesbeth — Wed, 23 Nov 2022 09:36:33 +0000

L. De Bruecker, V. Van Speybroeck

Inorganic Chemistry

61, 51, 20743–20756

2022

Abstract

The nucleation process of zeolitic imidazolate frameworks (ZIFs) is, to date, not yet completely understood, making the search for tailored materials very difficult. Recently, it has been shown that, during the formation process, the symmetry of the precursors is reduced by ligand elimination and substitution reactions. The octahedral precursors with simple ligands, such as water, methanol, and/or NO₃^–, are transformed to five- and finally four-coordinated complexes with imidazole ligands. This reduction of symmetry, caused both by the changing coordination environment and distortions from the perfect symmetry leading to another point group, will have a large influence on the electronic structure and more specifically on the d-orbital splitting. This, in turn, will affect the d–d electronic excitations, which can be followed using UV–vis spectroscopy and which can help to unravel the formation process. In this work, we systematically investigate how the lowering of the number of ligands affects the symmetry and thus the geometry and electronic structure of Co²⁺ complexes with six, five, and four aqua ligands. Therefore, we first resort to qualitative techniques, such as crystal field theory (CFT) and ligand field theory (LFT), which reveal that the orbital splitting is characteristic for the number of ligands. However, as these techniques are not capable of providing quantitative results without the use of experimental data as input, we perform various computational calculations. Both average of configuration (AOC) and unrestricted density functional theory (UDFT) are thoroughly investigated, and we will determine which technique is the best suited to properly describe the ground state of these systems. To investigate the dependency on the d-orbital occupation, we also investigated V²⁺, Mn²⁺, and Ni²⁺ hexa-aqua-complexes and compared them to the Co systems.

DOI

https://doi.org/10.1021/acs.inorgchem.2c02358

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acs.inorgchem.2c02358 (1).pdf

Structural and photophysical properties of various polypyridyl ligands: A combined experimental and computational study

liesbeth — Wed, 14 Oct 2020 15:28:15 +0000

L. De Bruecker, J. Everaert, P. Van der Voort, C.V. Stevens, M. Waroquier, V. Van Speybroeck

ChemPhysChem

21 (22), 2489–2505

2020

Abstract

Covalent triazine frameworks (CTFs) with polypyridyl ligands are very promising supports to anchor photocatalytic complexes. Herein, we investigate the photophysical properties of a series of ligands which vary by the extent of the aromatic system, the nitrogen content and their topologies to aid in selecting interesting building blocks for CTFs. Interestingly, some linkers have a rotational degree of freedom, allowing both a trans and cis structure, where only the latter allows anchoring. Therefore, the influence of the dihedral angle on the UV‐Vis spectrum is studied . The photophysical properties are investigated by a combined computational and experimental study. Theoretically, both static and molecular dynamics simulations are performed to deduce ground‐ and excited state properties based on density functional theory (DFT) and time‐dependent DFT. The position of the main absorption peak shifts towards higher wavelengths for an increased size of the π‐system and a higher π‐electron deficiency. We found that the position of the main absorption peak among the different ligands studied in this work can amount to 271 nm; which has a significant impact on the photophysical properties of the ligands. This broad range of shifts allows modulation of the electronic structure by varying the ligands and may help in a rational design of efficient photocatalysts.

Gold Open Access

DOI

https://doi.org/10.1002/cphc.202000592

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cphc.202000592.pdf

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

sven — Fri, 02 Aug 2019 15:36:39 +0000

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

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

Spectroscopic Fingerprint of Electronic Excitations in Nanoporous Frameworks and Transition Metal Complexes

mieke — Mon, 04 Sep 2023 09:04:57 +0000

L. De Bruecker

Tue, 29/08/2023

iGent tower, Technologiepark, Zwijnaarde

Supervisors

Prof. Dr. ir. V. Van Speybroeck

Attachment (private)

phdfinal-liesbethdebruecker-7_compressed.pdf

Computational Study of the Electronic Structure of Co2+ Aqua-Complexes

liesbeth — Mon, 05 Sep 2022 11:49:05 +0000

L. De Bruecker, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

DFT2022

Brussels Belgium

Monday, 29 August, 2022 to Friday, 2 September, 2022

Abstract (private)

DeBruecker_Abstract.pdf

Applying advanced quantum mechanical techniques to describe d-orbital excitations in highly correlated systems

leen — Thu, 24 Mar 2022 10:37:11 +0000

S. De Coen

Master of Science in Engineering Physics

2022

Supervisors

Prof. Dr. ir. Veronique Van Speybroeck

Operando Methods in Catalysis and Material Science

alexander — Mon, 13 Dec 2021 16:40:19 +0000

A.E.J. Hoffman, P. Cnudde, L. De Bruecker, S.M.J. Rogge, V. Van Speybroeck

Wiley-VCH

2023

ISBN

in press

Zeolite-catalyzed benzene ethylation: New mechanistic insights from an old-school reaction class

massimo — Wed, 21 Apr 2021 13:38:18 +0000

M. Bocus, L. De Bruecker, L. Vanduyfhuys, V. Van Speybroeck

ISBN/ISSN:

Talk

Conference / event / venue

ACS Spring 2021

Online

Monday, 5 April, 2021 to Friday, 30 April, 2021

Applying advanced quantum mechanical techniques to describe d-orbital excitations in highly correlated systems

leen — Mon, 01 Mar 2021 11:37:52 +0000