Photofunctionality of iron(III) N-heterocyclic carbenes and related d transition metal complexes

Chábera, Pavel; Lindh, Linnea; Rosemann, Nils W.; Prakash, Om; Uhlig, Jens; Yartsev, Arkady; Wärnmark, Kenneth; Sundström, Villy; Persson, Petter

doi:10.1016/j.ccr.2020.213517

Cited by 49 publications

(57 citation statements)

References 129 publications

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“…10 a by the shift in nuclear co-ordinates of the core-excited state. In the case of the iron–carbene complexes, this fits well with the established view of elongation of Fe–C bonds through population in the core-excited state of the anti-bonding level 8 . This is similar to a mechanism used to explain the vibrational structure of core excitations in small molecules such as 56 .…”

Section: Discussionsupporting

confidence: 87%

“…This is similar to a mechanism used to explain the vibrational structure of core excitations in small molecules such as 56 . Additionally, bond elongation in the iron carbenes is known to cause symmetry-breaking Jahn–Teller distortions in the metal-centred excited states 8 . This is reminiscent of the vibronic coupling model in the pseudo-Jahn–Teller case of 55 .…”

Section: Discussionmentioning

confidence: 99%

“…Additionally, a photo-active bimetallic / compound has been recently reported 18 . The photofunctionality of the complexes is particularly noteworthy given that the photo-excited Ligand-to-Metal CT (LMCT) excited states have only rarely shown useful photochemical properties for transition metal systems 8 .

Figure 1 Schemes of the two Fe-NHC complexes studied: (a) and (b) , where btz = 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy = 2,2’-bipyridine.…”

Section: Introductionmentioning

confidence: 99%

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Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Temperton

Guo

D’Acunto

et al. 2021

Sci Rep

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Two photoactive iron N-heterocyclic carbene complexes $${[\hbox {Fe}^{{{\rm{II}}}}(\hbox {btz})_2(\hbox {bpy})]^{2+}}$$ [ Fe II ( btz ) 2 ( bpy ) ] 2 + and $${[\hbox {Fe}^{{\rm{III}}}(\hbox {btz})_3]^{3+}}$$ [ Fe III ( btz ) 3 ] 3 + , where btz is 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2’-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-ray photon energy to match core-valence excitations provides a site specific probe of the electronic structure properties and ligand-field interactions, as well as information about the resonantly photo-oxidised final states. Comparing measurements of the Fe centre and the surrounding ligands demonstrate strong mixing of the Fe $${\hbox {t}_{{\rm{2g}}}}$$ t 2 g levels with occupied ligand $$\pi$$ π orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of $$\pi$$ π -accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity is also observed as a final-state effect in the RPES measurements of the open-shell $$\hbox {Fe}^{{\rm{III}}}$$ Fe III complex. Vibronic coupling is evident in both complexes, where the energy dispersion hints at a vibrationally hot final state. The results demonstrate the significant impact of the iron oxidation state on the frontier electronic structure and highlights the differences between the emerging class of $$\hbox {Fe}^{{\rm{III}}}$$ Fe III photosensitizers from those of more traditional $$\hbox {Fe}^{{\rm{II}}}$$ Fe II complexes.

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Section: Discussionsupporting

confidence: 87%

Section: Discussionmentioning

confidence: 99%

Figure 1 Schemes of the two Fe-NHC complexes studied: (a) and (b) , where btz = 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene) and bpy = 2,2’-bipyridine.…”

Section: Introductionmentioning

confidence: 99%

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Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Temperton

Guo

D’Acunto

et al. 2021

Sci Rep

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“…on copper( i ), 23,24 nickel(0, ii ), 25,26 cobalt( iii ), 27 iron( ii , iii ), 28–31 chromium(0/ iii ) 32–35 and vanadium( iii ). 36 Beyond the conventionally exploited MLCT excited states, 12 LMCT states of the low-spin d 5 electron configuration of iron( iii ) 18 and spin–flip states of the d 3 electron configuration of chromium( iii ) 15 are emerging as novel paradigmatic excited states useful for photoapplications.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry

et al. 2021

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“…NHCs are a very useful tool in modern organic synthesis, mainly due to their ability to bind most transition metals. Metal complexes with NHCs are homogeneous catalysts for many reactions (mainly as ruthenium and palladium complexes) [27,28]; additionally, NHCs themselves can be used as organocatalysts [29][30][31]. Moreover, it has been shown that NHC-metal complexes exhibit antibacterial and antitumor activity, especially when the NHCs are silver-or gold-bound ligands [32,33].…”

Section: Introductionmentioning

confidence: 99%

Steroid-Functionalized Imidazolium Salts with an Extended Spectrum of Antifungal and Antibacterial Activity

Malinowska

Sawicka

Niemirowicz-Laskowska

et al. 2021

IJMS

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It is established that high rates of morbidity and mortality caused by fungal infections are related to the current limited number of antifungal drugs and the toxicity of these agents. Imidazolium salts as azole derivatives can be successfully used in the treatment of fungal infections in humans. Steroid-functionalized imidazolium salts were synthesized using a new, more efficient method. As a result, 20 salts were obtained with high yields, 12 of which were synthesized and characterized for the first time. They were derivatives of lithocholic acid and 3-oxo-23,24-dinorchol-4-ene-22-al and were fully characterized by 1H and 13C nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and high resolution mass spectrometry (HRMS). Due to the excellent activity against bacteria and Candida albicans, new research was extended to include tests on five species of pathogenic fungi and molds: Aspergillus niger ATCC 16888, Aspergillus fumigatus ATCC 204305, Trichophyton mentagrophytes ATCC 9533, Cryptococcus neoformans ATCC 14116, and Microsporum canis ATCC 11621. The results showed that the new salts are almost universal antifungal agents and have a broad spectrum of activity against other human pathogens. To initially assess the safety of the synthesized salts, hemocompatibility with host cells and cytotoxicity were also examined. No toxicity was observed at the concentration at which the compounds were active against pathogens.

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Photofunctionality of iron(III) N-heterocyclic carbenes and related d transition metal complexes

Cited by 49 publications

References 129 publications

Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes

Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry

Steroid-Functionalized Imidazolium Salts with an Extended Spectrum of Antifungal and Antibacterial Activity

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