--- _id: '60600' abstract: - lang: eng text: In the search for noble metal free photocatalytic systems, iron is the dream candidate. To increase excited state lifetimes of iron complexes, the multichromophoric approach is promising, combining organic chromophores with photoactive iron complexes, potentially enabling a reservoir effect. We present a series of chromophore-functionalized complexes based on the parental FeIII complex [Fe(ImP)2][PF6] (HImP = 1,1′-(1,3-phenylene)bis(3-methyl-1-imidazole-2-ylidene)). The four organic chromophores benzene, naphthalene, anthracene, and pyrene are attached to the ImP-ligand in para-position to the coordination site to systematically investigate the influence of the steric demand and electronic properties of the chromophore on charge transfer lifetimes as well as photodynamics. A thorough ground state characterization was conducted in addition to investigations of the excited state dynamics by transient absorption spectroscopy and streak camera emission measurements. The conclusions drawn are supported by extensive DFT calculations. The emission coefficients could be significantly improved by the addition of chromophores. After excitation of the complexes with larger chromophores, coplanarization of the backbone and complex motif occurs to stabilize the formal charge. This results in population of a superligand state that exhibits a much faster radiationless relaxation to the ground state compared to the parent complex, hindering a reservoir effect. article_number: acs.inorgchem.5c00526 author: - first_name: Lennart full_name: Schmitz, Lennart id: '53140' last_name: Schmitz - first_name: Miguel A. full_name: Argüello Cordero, Miguel A. last_name: Argüello Cordero - first_name: Mohammed J. full_name: Al-Marri, Mohammed J. last_name: Al-Marri - first_name: Roland full_name: Schoch, Roland id: '48467' last_name: Schoch orcid: 0000-0003-2061-7289 - first_name: Hans full_name: Egold, Hans id: '101' last_name: Egold - first_name: Adam full_name: Neuba, Adam last_name: Neuba - first_name: Jakob full_name: Steube, Jakob id: '40342' last_name: Steube orcid: 0000-0003-3178-4429 - first_name: Bastian Johannes full_name: Bracht, Bastian Johannes id: '86707' last_name: Bracht - first_name: Olga S. full_name: Bokareva, Olga S. last_name: Bokareva - first_name: Stefan full_name: Lochbrunner, Stefan last_name: Lochbrunner - first_name: Matthias full_name: Bauer, Matthias id: '47241' last_name: Bauer orcid: 0000-0002-9294-6076 citation: ama: Schmitz L, Argüello Cordero MA, Al-Marri MJ, et al. Chromophore Induced Effects in Iron(III) Complexes. Inorganic Chemistry. Published online 2025. doi:10.1021/acs.inorgchem.5c00526 apa: Schmitz, L., Argüello Cordero, M. A., Al-Marri, M. J., Schoch, R., Egold, H., Neuba, A., Steube, J., Bracht, B. J., Bokareva, O. S., Lochbrunner, S., & Bauer, M. (2025). Chromophore Induced Effects in Iron(III) Complexes. Inorganic Chemistry, Article acs. inorgchem.5c00526. https://doi.org/10.1021/acs.inorgchem.5c00526 bibtex: '@article{Schmitz_Argüello Cordero_Al-Marri_Schoch_Egold_Neuba_Steube_Bracht_Bokareva_Lochbrunner_et al._2025, title={Chromophore Induced Effects in Iron(III) Complexes}, DOI={10.1021/acs.inorgchem.5c00526}, number={acs. inorgchem.5c00526}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Schmitz, Lennart and Argüello Cordero, Miguel A. and Al-Marri, Mohammed J. and Schoch, Roland and Egold, Hans and Neuba, Adam and Steube, Jakob and Bracht, Bastian Johannes and Bokareva, Olga S. and Lochbrunner, Stefan and et al.}, year={2025} }' chicago: Schmitz, Lennart, Miguel A. Argüello Cordero, Mohammed J. Al-Marri, Roland Schoch, Hans Egold, Adam Neuba, Jakob Steube, et al. “Chromophore Induced Effects in Iron(III) Complexes.” Inorganic Chemistry, 2025. https://doi.org/10.1021/acs.inorgchem.5c00526. ieee: 'L. Schmitz et al., “Chromophore Induced Effects in Iron(III) Complexes,” Inorganic Chemistry, Art. no. acs. inorgchem.5c00526, 2025, doi: 10.1021/acs.inorgchem.5c00526.' mla: Schmitz, Lennart, et al. “Chromophore Induced Effects in Iron(III) Complexes.” Inorganic Chemistry, acs. inorgchem.5c00526, American Chemical Society (ACS), 2025, doi:10.1021/acs.inorgchem.5c00526. short: L. Schmitz, M.A. Argüello Cordero, M.J. Al-Marri, R. Schoch, H. Egold, A. Neuba, J. Steube, B.J. Bracht, O.S. Bokareva, S. Lochbrunner, M. Bauer, Inorganic Chemistry (2025). date_created: 2025-07-14T08:49:25Z date_updated: 2025-08-15T12:18:08Z department: - _id: '306' doi: 10.1021/acs.inorgchem.5c00526 keyword: - Photo language: - iso: eng publication: Inorganic Chemistry publication_identifier: issn: - 0020-1669 - 1520-510X publication_status: published publisher: American Chemical Society (ACS) status: public title: Chromophore Induced Effects in Iron(III) Complexes type: journal_article user_id: '48467' year: '2025' ... --- _id: '56947' abstract: - lang: eng text: Pore engineering is commonly used to alter the properties of metal–organic frameworks. This is achieved by incorporating different linker molecules (L) into the structure, generating isoreticular frameworks. CPO-27, also named MOF-74, is a prototypical material for this approach, offering the potential to modify the size of its one-dimensional pore channels and the hydrophobicity of pore walls using various linker ligands during synthesis. Thermal activation of these materials yields accessible open metal sites (i.e., under-coordinated metal centers) at the pore walls, thus acting as strong primary binding sites for guest molecules, including water. We study the effect of the pore size and linker hydrophobicity within a series of Ni2+-based isoreticular frameworks (i.e., Ni2L, L = dhtp, dhip, dondc, bpp, bpm, tpp), analyzing their water sorption behavior and the water interactions in the confined pore space. For this purpose, we apply water vapor sorption analysis and Fourier transform infrared spectroscopy. In addition, defect degrees of all compounds are determined by thermogravimetric analysis and solution 1H nuclear magnetic resonance spectroscopy. We find that larger defect degrees affect the preferential sorption sites in Ni2dhtp, while no such indication is found for the other materials in our study. Instead, strong evidence is found for the formation of water bridges/chains between coordinating water molecules, as previously observed for hydrophobic porous carbons and mesoporous silica. This suggests similar sorption energies for additional water molecules in materials with larger pore sizes after saturation of the primary binding sites, resulting in more bulk-like water arrangements. Consequently, the sorption mechanism is driven by classical pore condensation through H-bonding anchor sites instead of sorption at discrete sites. article_type: original author: - first_name: Marvin full_name: Kloß, Marvin last_name: Kloß - first_name: Lara full_name: Schäfers, Lara last_name: Schäfers - first_name: Zhenyu full_name: Zhao, Zhenyu last_name: Zhao - first_name: Christian full_name: Weinberger, Christian id: '11848' last_name: Weinberger - first_name: Hans full_name: Egold, Hans id: '101' last_name: Egold - first_name: Michael full_name: Tiemann, Michael id: '23547' last_name: Tiemann orcid: 0000-0003-1711-2722 citation: ama: 'Kloß M, Schäfers L, Zhao Z, Weinberger C, Egold H, Tiemann M. Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation. Nanomaterials. 2024;14(22):1791. doi:10.3390/nano14221791' apa: 'Kloß, M., Schäfers, L., Zhao, Z., Weinberger, C., Egold, H., & Tiemann, M. (2024). Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation. Nanomaterials, 14(22), 1791. https://doi.org/10.3390/nano14221791' bibtex: '@article{Kloß_Schäfers_Zhao_Weinberger_Egold_Tiemann_2024, title={Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation}, volume={14}, DOI={10.3390/nano14221791}, number={22}, journal={Nanomaterials}, publisher={MDPI AG}, author={Kloß, Marvin and Schäfers, Lara and Zhao, Zhenyu and Weinberger, Christian and Egold, Hans and Tiemann, Michael}, year={2024}, pages={1791} }' chicago: 'Kloß, Marvin, Lara Schäfers, Zhenyu Zhao, Christian Weinberger, Hans Egold, and Michael Tiemann. “Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation.” Nanomaterials 14, no. 22 (2024): 1791. https://doi.org/10.3390/nano14221791.' ieee: 'M. Kloß, L. Schäfers, Z. Zhao, C. Weinberger, H. Egold, and M. Tiemann, “Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation,” Nanomaterials, vol. 14, no. 22, p. 1791, 2024, doi: 10.3390/nano14221791.' mla: 'Kloß, Marvin, et al. “Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation.” Nanomaterials, vol. 14, no. 22, MDPI AG, 2024, p. 1791, doi:10.3390/nano14221791.' short: M. Kloß, L. Schäfers, Z. Zhao, C. Weinberger, H. Egold, M. Tiemann, Nanomaterials 14 (2024) 1791. date_created: 2024-11-08T06:18:11Z date_updated: 2025-01-10T14:27:39Z department: - _id: '35' - _id: '2' - _id: '307' doi: 10.3390/nano14221791 intvolume: ' 14' issue: '22' language: - iso: eng main_file_link: - open_access: '1' oa: '1' page: '1791' publication: Nanomaterials publication_identifier: issn: - 2079-4991 publication_status: published publisher: MDPI AG quality_controlled: '1' status: public title: 'Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation' type: journal_article user_id: '23547' volume: 14 year: '2024' ... --- _id: '56075' abstract: - lang: eng text: An isostructural series of FeII, FeIII, and Fe(IV)complexes [Fe(ImP)2]0/+/2+ utilizing the ImP 1,1′-(1,3-phenylene)-bis(3-methyl-1-imidazol-2-ylidene) ligand, combining N-heterocy-clic carbenes and cyclometalating functions, is presented. The strong donor motif stabilizes the high-valent Fe(IV) oxidation state yet keeps the FeII oxidation state accessible from the parent Fe(III)compound. Chemical oxidation of [Fe(ImP)2]+ yields stable [FeIV(ImP)2]2+. In contrast, [FeII(ImP)2]0, obtained by reduction,is highly sensitive toward oxygen. Exhaustive ground state characterization by single-crystal X-ray diffraction, 1H NMR,Mössbauer spectroscopy, temperature-dependent magnetic measurements, a combination of X-ray absorption near edge structureand valence-to-core, as well as core-to-core X-ray emission spectroscopy, complemented by detailed density functional theory (DFT) analysis, reveals that the three complexes[Fe(ImP)2]0/+/2+ can be unequivocally attributed to low-spin d6, d5, and d4 complexes. The excited state landscape of the Fe(II) and Fe(IV) complexes is characterized by short-lived 3MLCT and 3LMCT states, with lifetimes of 5.1 and 1.4 ps, respectively. In the FeII-compound, an energetically low-lying MC state leads to fast deactivation of the MLCT state. The distorted square-pyramidal state, where one carbene is dissociated, can not only relax into the ground state, but also into a singlet dissociated state. Its formation was investigated with time-dependent optical spectroscopy, while insights into its structure were gained by NMR spectroscopy. author: - first_name: Jakob full_name: Steube, Jakob id: '40342' last_name: Steube orcid: 0000-0003-3178-4429 - first_name: Lorena full_name: Fritsch, Lorena id: '44418' last_name: Fritsch - first_name: Ayla full_name: Kruse, Ayla last_name: Kruse - first_name: Olga S. full_name: Bokareva, Olga S. last_name: Bokareva - first_name: Serhiy full_name: Demeshko, Serhiy last_name: Demeshko - first_name: Hossam full_name: Elgabarty, Hossam id: '60250' last_name: Elgabarty orcid: 0000-0002-4945-1481 - first_name: Roland full_name: Schoch, Roland id: '48467' last_name: Schoch orcid: 0000-0003-2061-7289 - first_name: Mohammad full_name: Alaraby, Mohammad last_name: Alaraby - first_name: Hans full_name: Egold, Hans id: '101' last_name: Egold - first_name: Bastian Johannes full_name: Bracht, Bastian Johannes id: '86707' last_name: Bracht - first_name: Lennart full_name: Schmitz, Lennart id: '53140' last_name: Schmitz - first_name: Stephan full_name: Hohloch, Stephan last_name: Hohloch - first_name: Thomas D. full_name: Kühne, Thomas D. last_name: Kühne - first_name: Franc full_name: Meyer, Franc last_name: Meyer - first_name: Oliver full_name: Kühn, Oliver last_name: Kühn - first_name: Stefan full_name: Lochbrunner, Stefan last_name: Lochbrunner - first_name: Matthias full_name: Bauer, Matthias id: '47241' last_name: Bauer orcid: 0000-0002-9294-6076 citation: ama: Steube J, Fritsch L, Kruse A, et al. Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States. Inorganic Chemistry. Published online 2024. doi:10.1021/acs.inorgchem.4c02576 apa: Steube, J., Fritsch, L., Kruse, A., Bokareva, O. S., Demeshko, S., Elgabarty, H., Schoch, R., Alaraby, M., Egold, H., Bracht, B. J., Schmitz, L., Hohloch, S., Kühne, T. D., Meyer, F., Kühn, O., Lochbrunner, S., & Bauer, M. (2024). Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States. Inorganic Chemistry. https://doi.org/10.1021/acs.inorgchem.4c02576 bibtex: '@article{Steube_Fritsch_Kruse_Bokareva_Demeshko_Elgabarty_Schoch_Alaraby_Egold_Bracht_et al._2024, title={Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States}, DOI={10.1021/acs.inorgchem.4c02576}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Steube, Jakob and Fritsch, Lorena and Kruse, Ayla and Bokareva, Olga S. and Demeshko, Serhiy and Elgabarty, Hossam and Schoch, Roland and Alaraby, Mohammad and Egold, Hans and Bracht, Bastian Johannes and et al.}, year={2024} }' chicago: Steube, Jakob, Lorena Fritsch, Ayla Kruse, Olga S. Bokareva, Serhiy Demeshko, Hossam Elgabarty, Roland Schoch, et al. “Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States.” Inorganic Chemistry, 2024. https://doi.org/10.1021/acs.inorgchem.4c02576. ieee: 'J. Steube et al., “Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States,” Inorganic Chemistry, 2024, doi: 10.1021/acs.inorgchem.4c02576.' mla: Steube, Jakob, et al. “Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States.” Inorganic Chemistry, American Chemical Society (ACS), 2024, doi:10.1021/acs.inorgchem.4c02576. short: J. Steube, L. Fritsch, A. Kruse, O.S. Bokareva, S. Demeshko, H. Elgabarty, R. Schoch, M. Alaraby, H. Egold, B.J. Bracht, L. Schmitz, S. Hohloch, T.D. Kühne, F. Meyer, O. Kühn, S. Lochbrunner, M. Bauer, Inorganic Chemistry (2024). date_created: 2024-09-05T11:34:20Z date_updated: 2025-08-15T12:17:35Z department: - _id: '306' doi: 10.1021/acs.inorgchem.4c02576 keyword: - Photo language: - iso: eng publication: Inorganic Chemistry publication_identifier: issn: - 0020-1669 - 1520-510X publication_status: published publisher: American Chemical Society (ACS) status: public title: Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States type: journal_article user_id: '48467' year: '2024' ... --- _id: '46548' abstract: - lang: eng text: The use of iron as a replacement for noble metals in photochemical and photophysical applications is challenging due to the typically fast deactivation of short-lived catalytically active states. Recent success of a cyclometalated iron(III) complex utilizing a bis-tridentate ligand motif inspired the use of phenyl-1H-pyrazole as a bidentate ligand. Five complexes using the tris(1-phenylpyrazolato-N,C2)iron(III) complex scaffold are presented. In addition to the parent complex, four derivatives with functionalization in the meta-position of the phenyl ring are thoroughly investigated by single crystal diffractometry, UV-Vis-spectroscopy, and cyclic voltammetry. Advanced X-ray spectroscopy in the form of X-ray absorption and emission spectroscopy allows unique insights into the electronic structure as well as DFT calculations. The ligand design leads to overlapping MLCT and LMCT absorption bands, and emissive behavior is suppressed by low-lying MC states. article_number: '282' author: - first_name: Tanja full_name: Hirschhausen, Tanja last_name: Hirschhausen - first_name: Lorena full_name: Fritsch, Lorena id: '44418' last_name: Fritsch - first_name: Franziska full_name: Lux, Franziska last_name: Lux - first_name: Jakob full_name: Steube, Jakob id: '40342' last_name: Steube orcid: 0000-0003-3178-4429 - first_name: Roland full_name: Schoch, Roland id: '48467' last_name: Schoch orcid: 0000-0003-2061-7289 - first_name: Adam full_name: Neuba, Adam last_name: Neuba - first_name: Hans full_name: Egold, Hans id: '101' last_name: Egold - first_name: Matthias full_name: Bauer, Matthias id: '47241' last_name: Bauer orcid: 0000-0002-9294-6076 citation: ama: Hirschhausen T, Fritsch L, Lux F, et al. Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands. Inorganics. 2023;11(7). doi:10.3390/inorganics11070282 apa: Hirschhausen, T., Fritsch, L., Lux, F., Steube, J., Schoch, R., Neuba, A., Egold, H., & Bauer, M. (2023). Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands. Inorganics, 11(7), Article 282. https://doi.org/10.3390/inorganics11070282 bibtex: '@article{Hirschhausen_Fritsch_Lux_Steube_Schoch_Neuba_Egold_Bauer_2023, title={Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands}, volume={11}, DOI={10.3390/inorganics11070282}, number={7282}, journal={Inorganics}, publisher={MDPI AG}, author={Hirschhausen, Tanja and Fritsch, Lorena and Lux, Franziska and Steube, Jakob and Schoch, Roland and Neuba, Adam and Egold, Hans and Bauer, Matthias}, year={2023} }' chicago: Hirschhausen, Tanja, Lorena Fritsch, Franziska Lux, Jakob Steube, Roland Schoch, Adam Neuba, Hans Egold, and Matthias Bauer. “Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands.” Inorganics 11, no. 7 (2023). https://doi.org/10.3390/inorganics11070282. ieee: 'T. Hirschhausen et al., “Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands,” Inorganics, vol. 11, no. 7, Art. no. 282, 2023, doi: 10.3390/inorganics11070282.' mla: Hirschhausen, Tanja, et al. “Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands.” Inorganics, vol. 11, no. 7, 282, MDPI AG, 2023, doi:10.3390/inorganics11070282. short: T. Hirschhausen, L. Fritsch, F. Lux, J. Steube, R. Schoch, A. Neuba, H. Egold, M. Bauer, Inorganics 11 (2023). date_created: 2023-08-16T14:44:37Z date_updated: 2025-08-15T12:54:21Z doi: 10.3390/inorganics11070282 intvolume: ' 11' issue: '7' keyword: - Photo language: - iso: eng publication: Inorganics publication_identifier: issn: - 2304-6740 publication_status: published publisher: MDPI AG status: public title: Iron(III)-Complexes with N-Phenylpyrazole-Based Ligands type: journal_article user_id: '48467' volume: 11 year: '2023' ...