Variable electronic structure and spin distribution in bis(2,2′-bipyridine)-metal complexes (M = Ru or Os) of 4,5-dioxido- and 4,5-diimido-pyrene

The odd-electron compounds [M(bpy) 2 (L 1 )](ClO 4 ) M = Ru ([ 1 ](ClO 4 )) or Os ([ 2 ](ClO 4 )), and the even-electron species [M(bpy) 2 (H 2 L 2 )](ClO 4 ) 2 , M = Ru ([ 3 ](ClO 4 ) 2 ) or Os ([ 4 ](ClO 4 ) 2 ) were obtained from pyrene-4,5-dione, L 1 , or 4,5-diaminopyrene, H 4 L 2 , and were ch...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 5; no. 12; pp. 4191 - 421
Main Authors Chatterjee, Madhumita, Mondal, Sudipta, Hazari, Arijit Singha, Záliš, Stanislav, Kaim, Wolfgang, Lahiri, Goutam Kumar
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 28.03.2021
Subjects
Coordination compounds
Crystallography
Electron spin
Electron transitions
Electronic spectra
Electronic structure
Electrons
Format
Mass spectra
Mathematical analysis
NMR
Nuclear magnetic resonance
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Summary:The odd-electron compounds [M(bpy) 2 (L 1 )](ClO 4 ) M = Ru ([ 1 ](ClO 4 )) or Os ([ 2 ](ClO 4 )), and the even-electron species [M(bpy) 2 (H 2 L 2 )](ClO 4 ) 2 , M = Ru ([ 3 ](ClO 4 ) 2 ) or Os ([ 4 ](ClO 4 ) 2 ) were obtained from pyrene-4,5-dione, L 1 , or 4,5-diaminopyrene, H 4 L 2 , and were characterised structurally, electrochemically and spectroscopically. Experimental and computational analysis (TD-DFT) revealed rather different electronic structures and spin distributions of the paramagnetic monocations 1 + -4 + . EPR investigations and electronic absorption studies exhibit increasing metal contributions to the singly occupied MO along the series 1 + < 3 + < 4 + < 2 + , illustrated by g value and long-wavelength absorbance. In addition to variations of the metal (Ru,Os) and the donor atoms (O,NH) the extension of the π system of the semiquinone-type ligand has a large effect on the electronic structure of the paramagnetic cations. Electronic structure variation in metal/ o -quinone orbital mixed systems [M(L)(bpy) 2 ] x can be systematically effected by extending the π system (benzene/pyrene), by changing the donors (O/NH) and by substituting the metal centers (Ru/Os).
Bibliography:10.1039/d1dt00282a
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mass spectra (Fig. S1), NMR (Fig. S2, S3), ORTEP (Fig. S4, S5), DFT optimised structure (Fig. S6), EPR (Fig. S7), DFT calculated mulliken spin density plot (Fig. S8), TD-DFT simulated electronic spectra (Fig. S9, S10), theoretical excitation plot (Fig. S11-S14), crystallographic data (Table S1), DFT calculated bond lengths and angles (Tables S2-S13), DFT calculated energies (Table S14), DFT calculated mulliken spin densities (Table S15), experimental and TD-DFT calculated electronic transitions (Tables S16-S19), and MO compositions (Tables S20-S41), CCDC
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For ESI and crystallographic data in CIF or other electronic format see DOI
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2008486
Electronic supplementary information (ESI) available: X-ray crystallographic files in CIF format for
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2008487
2008484
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2008485
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ISSN:1477-9226
1477-9234
DOI:10.1039/d1dt00282a