Photophysical Integrity of the Iron(III) Scorpionate Framework in Iron(III)-NHC Complexes with Long-Lived 2LMCT Excited States
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Photophysical Integrity of the Iron(III) Scorpionate Framework in Iron(III)-NHC Complexes with Long-Lived 2LMCT Excited States. / Prakash, Om; Lindh, Linnea; Kaul, Nidhi; Rosemann, Nils W.; Losada, Iria Bolano; Johnson, Catherine; Chabera, Pavel; Ilic, Aleksandra; Schwarz, Jesper; Gupta, Arvind Kumar; Uhlig, Jens; Ericsson, Tore; Haggstrom, Lennart; Huang, Ping; Bendix, Jesper; Strand, Daniel; Yartsev, Arkady; Lomoth, Reiner; Persson, Petter; Warnmark, Kenneth.
I: Inorganic Chemistry, Bind 61, Nr. 44, 2022, s. 17515–17526.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Photophysical Integrity of the Iron(III) Scorpionate Framework in Iron(III)-NHC Complexes with Long-Lived 2LMCT Excited States
AU - Prakash, Om
AU - Lindh, Linnea
AU - Kaul, Nidhi
AU - Rosemann, Nils W.
AU - Losada, Iria Bolano
AU - Johnson, Catherine
AU - Chabera, Pavel
AU - Ilic, Aleksandra
AU - Schwarz, Jesper
AU - Gupta, Arvind Kumar
AU - Uhlig, Jens
AU - Ericsson, Tore
AU - Haggstrom, Lennart
AU - Huang, Ping
AU - Bendix, Jesper
AU - Strand, Daniel
AU - Yartsev, Arkady
AU - Lomoth, Reiner
AU - Persson, Petter
AU - Warnmark, Kenneth
PY - 2022
Y1 - 2022
N2 - Fe(III) complexes with N-heterocyclic carbene (NHC) ligands belong to the rare examples of Earth-abundant transition metal complexes with long-lived luminescent charge-transfer excited states that enable applications as photosensitizers for charge separation reactions. We report three new hexa-NHC complexes of this class: [Fe(brphtmeimb)2]PF6 (brphtmeimb = [(4-bromophenyl)tris(3-methylimidazol-2-ylidene)borate]- , [Fe-(meophtmeimb)2]PF6 (meophtmeimb = [(4-methoxyphenyl)tris-(3-methylimidazol-2-ylidene)borate] -, and [Fe-(coohphtmeimb)2]PF6 (coohphtmeimb = [(4-carboxyphenyl)tris-(3-methylimidazol-2-ylidene)borate]-. These were derived from the parent complex [Fe(phtmeimb)2]PF6 (phtmeimb = [phenyltris(3-methylimidazol-2-ylidene)borate]- by modification with electron-withdrawing and electron-donating substituents, respectively, at the 4-phenyl position of the ligand framework. All three Fe(III) hexa-NHC complexes were characterized by NMR spectroscopy, high-resolution mass spectroscopy, elemental analysis, single crystal X-ray diffraction analysis, electrochemistry, Mo''ssbauer spectroscopy, electronic spectroscopy, magnetic susceptibility measurements, and quantum chemical calculations. Their ligand-to-metal charge-transfer (2LMCT) excited states feature nanosecond lifetimes (1.6-1.7 ns) and sizable emission quantum yields (1.7-1.9%) through spin-allowed transition to the doublet ground state (2GS), completely in line with the parent complex [Fe(phtmeimb)2]PF6 (2.0 ns and 2.1%). The integrity of the favorable excited state characteristics upon substitution of the ligand framework demonstrates the robustness of the scorpionate motif that tolerates modifications in the 4-phenyl position for applications such as the attachment in molecular or hybrid assemblies.
AB - Fe(III) complexes with N-heterocyclic carbene (NHC) ligands belong to the rare examples of Earth-abundant transition metal complexes with long-lived luminescent charge-transfer excited states that enable applications as photosensitizers for charge separation reactions. We report three new hexa-NHC complexes of this class: [Fe(brphtmeimb)2]PF6 (brphtmeimb = [(4-bromophenyl)tris(3-methylimidazol-2-ylidene)borate]- , [Fe-(meophtmeimb)2]PF6 (meophtmeimb = [(4-methoxyphenyl)tris-(3-methylimidazol-2-ylidene)borate] -, and [Fe-(coohphtmeimb)2]PF6 (coohphtmeimb = [(4-carboxyphenyl)tris-(3-methylimidazol-2-ylidene)borate]-. These were derived from the parent complex [Fe(phtmeimb)2]PF6 (phtmeimb = [phenyltris(3-methylimidazol-2-ylidene)borate]- by modification with electron-withdrawing and electron-donating substituents, respectively, at the 4-phenyl position of the ligand framework. All three Fe(III) hexa-NHC complexes were characterized by NMR spectroscopy, high-resolution mass spectroscopy, elemental analysis, single crystal X-ray diffraction analysis, electrochemistry, Mo''ssbauer spectroscopy, electronic spectroscopy, magnetic susceptibility measurements, and quantum chemical calculations. Their ligand-to-metal charge-transfer (2LMCT) excited states feature nanosecond lifetimes (1.6-1.7 ns) and sizable emission quantum yields (1.7-1.9%) through spin-allowed transition to the doublet ground state (2GS), completely in line with the parent complex [Fe(phtmeimb)2]PF6 (2.0 ns and 2.1%). The integrity of the favorable excited state characteristics upon substitution of the ligand framework demonstrates the robustness of the scorpionate motif that tolerates modifications in the 4-phenyl position for applications such as the attachment in molecular or hybrid assemblies.
KW - HETEROCYCLIC CARBENE COMPLEXES
KW - LIGAND
KW - PHOTOSENSITIZERS
KW - PERSPECTIVE
KW - TIO2
KW - IRON
U2 - 10.1021/acs.inorgchem.2c02410
DO - 10.1021/acs.inorgchem.2c02410
M3 - Journal article
C2 - 36279568
VL - 61
SP - 17515
EP - 17526
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 44
ER -
ID: 325836393