Poster presentation: "Spin states of Mn(II) and Fe(III) complexes with thiosemicarbazone"
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Mn(II) and Fe(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole have been synthesized and characterized by single-crystal X-ray diffraction. Two complexes have the same ligand system – bis tridentate coordination of the thiosemicarbazone ligand through the NNS donor set of atoms. Furthermore, the central metal ions in both cases have the same d5 electronic configuration. However, measured magnetism and analysis of the crystal geometries show that these two complexes have a different number of unpaired electrons. We rationalized the results by electronic structure calculations based on density functional theory. High-spin Mn(II) complex has trigonal-prismatic geometry with ionic metal-ligand bonding. Hund's rule of maximum multiplicity is responsible for its sextet spin-ground state. On the other hand, low-spin Fe(III) complex has octahedral coordination and strong metal-ligand covalency with delocalization of spin density toward ligands. Low-spin, doubl...et state is favored because of the nephelauxetic effect, i.e., smaller pairing energy in Fe(III) complex. Our results show that the difference in the electronic structure of the two complexes, i.e., different spin-ground states, directly affects these molecules' structure, magnetism, reactivity, and biological activities.
Ključne reči:
spin states / metal-ligand bonding / Mn(II) / Fe(III) / transition metal complexes / coordination chemistry / geometries / spin densityIzvor:
2023Izdavač:
- TMMagCat Project
Finansiranje / projekti:
- TMMagCat - Tailoring Molecular Magnets and Catalysts Based on Transition Metal Complexes (RS-ScienceFundRS-Ideje-7750288)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200026 (Univerzitet u Beogradu, Institut za hemiju, tehnologiju i metalurgiju - IHTM) (RS-MESTD-inst-2020-200026)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200168 (Univerzitet u Beogradu, Hemijski fakultet) (RS-MESTD-inst-2020-200168)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200288 (Inovacioni centar Hemijskog fakulteta u Beogradu doo) (RS-MESTD-inst-2020-200288)
Napomena:
- Poster presentation at 6th EuChemS Inorganic Chemistry Conference, September 3 – 7, 2023, Institute of Applied Synthetic Chemistry, TU Wien, Austria, https://www.eicc6.at/
- Abstract: https://cer.ihtm.bg.ac.rs/handle/123456789/6570
Povezane informacije:
- Povezani sadržaj
https://cer.ihtm.bg.ac.rs/handle/123456789/6570
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Institucija/grupa
IHTMTY - CONF AU - Savić, Milica AU - Jevtović, Mima AU - Čobeljić, Božidar AU - Gruden, Maja AU - Zlatar, Matija PY - 2023 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/6572 AB - Mn(II) and Fe(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole have been synthesized and characterized by single-crystal X-ray diffraction. Two complexes have the same ligand system – bis tridentate coordination of the thiosemicarbazone ligand through the NNS donor set of atoms. Furthermore, the central metal ions in both cases have the same d5 electronic configuration. However, measured magnetism and analysis of the crystal geometries show that these two complexes have a different number of unpaired electrons. We rationalized the results by electronic structure calculations based on density functional theory. High-spin Mn(II) complex has trigonal-prismatic geometry with ionic metal-ligand bonding. Hund's rule of maximum multiplicity is responsible for its sextet spin-ground state. On the other hand, low-spin Fe(III) complex has octahedral coordination and strong metal-ligand covalency with delocalization of spin density toward ligands. Low-spin, doublet state is favored because of the nephelauxetic effect, i.e., smaller pairing energy in Fe(III) complex. Our results show that the difference in the electronic structure of the two complexes, i.e., different spin-ground states, directly affects these molecules' structure, magnetism, reactivity, and biological activities. PB - TMMagCat Project T1 - Poster presentation: "Spin states of Mn(II) and Fe(III) complexes with thiosemicarbazone" UR - https://hdl.handle.net/21.15107/rcub_cer_6572 ER -
@conference{ author = "Savić, Milica and Jevtović, Mima and Čobeljić, Božidar and Gruden, Maja and Zlatar, Matija", year = "2023", abstract = "Mn(II) and Fe(III) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole have been synthesized and characterized by single-crystal X-ray diffraction. Two complexes have the same ligand system – bis tridentate coordination of the thiosemicarbazone ligand through the NNS donor set of atoms. Furthermore, the central metal ions in both cases have the same d5 electronic configuration. However, measured magnetism and analysis of the crystal geometries show that these two complexes have a different number of unpaired electrons. We rationalized the results by electronic structure calculations based on density functional theory. High-spin Mn(II) complex has trigonal-prismatic geometry with ionic metal-ligand bonding. Hund's rule of maximum multiplicity is responsible for its sextet spin-ground state. On the other hand, low-spin Fe(III) complex has octahedral coordination and strong metal-ligand covalency with delocalization of spin density toward ligands. Low-spin, doublet state is favored because of the nephelauxetic effect, i.e., smaller pairing energy in Fe(III) complex. Our results show that the difference in the electronic structure of the two complexes, i.e., different spin-ground states, directly affects these molecules' structure, magnetism, reactivity, and biological activities.", publisher = "TMMagCat Project", title = "Poster presentation: "Spin states of Mn(II) and Fe(III) complexes with thiosemicarbazone"", url = "https://hdl.handle.net/21.15107/rcub_cer_6572" }
Savić, M., Jevtović, M., Čobeljić, B., Gruden, M.,& Zlatar, M.. (2023). Poster presentation: "Spin states of Mn(II) and Fe(III) complexes with thiosemicarbazone". TMMagCat Project.. https://hdl.handle.net/21.15107/rcub_cer_6572
Savić M, Jevtović M, Čobeljić B, Gruden M, Zlatar M. Poster presentation: "Spin states of Mn(II) and Fe(III) complexes with thiosemicarbazone". 2023;. https://hdl.handle.net/21.15107/rcub_cer_6572 .
Savić, Milica, Jevtović, Mima, Čobeljić, Božidar, Gruden, Maja, Zlatar, Matija, "Poster presentation: "Spin states of Mn(II) and Fe(III) complexes with thiosemicarbazone"" (2023), https://hdl.handle.net/21.15107/rcub_cer_6572 .