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Ruthenocene‐Type Complexes of N‐Fused Porphyrins
Author(s) -
Toganoh Motoki,
Matsuo Hideaki,
Sato Ayumi,
Furuta Hiroyuki
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600813
Subject(s) - homo/lumo , porphyrin , moiety , ruthenocene , chemistry , cyclopentadienyl complex , ligand (biochemistry) , ruthenium , conjugated system , stereochemistry , crystallography , photochemistry , molecule , ferrocene , organic chemistry , electrochemistry , biochemistry , receptor , polymer , electrode , catalysis
Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp 2 ] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.