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Synthesis, Aromaticity and Photophysical Behaviour of Ferrocene‐ and Ruthenocene‐Appended Semisynthetic Chlorin Derivatives
Author(s) -
Nikkonen Taru,
Moreno Oliva María,
Taubert Stefan,
Melchionna Michele,
Kahnt Axel,
Helaja Juho
Publication year - 2015
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.201501856
Subject(s) - chemistry , chlorin , metallocene , ruthenocene , aromaticity , photochemistry , deprotonation , ring (chemistry) , ferrocene , moiety , reactivity (psychology) , antiaromaticity , nucleophile , derivative (finance) , medicinal chemistry , porphyrin , stereochemistry , organic chemistry , electrochemistry , molecule , ion , polymerization , alternative medicine , pathology , financial economics , polymer , catalysis , medicine , electrode , economics
Two novel synthetic strategies to covalently link a metallocene electron‐donor unit to a chlorin ring are presented. In one approach, pyropheophorbide a is readily converted into its 13 1 ‐ferrocenyl dehydro derivative by nucleophilic addition of the ferrocenyl anion to the 13 1 ‐carbonyl group. In another approach, the corresponding 13 1 ‐pentamethylruthenocenyl derivative is synthesised from 13 1 ‐fulvenylchlorin by a facile ligand exchange/deprotonation reaction with the [RuCp*(cod)Cl] (Cp*=pentamethylcyclopentadienyl; cod=1,5‐cyclooctadiene) complex. The resulting metallocene–chlorins exhibit reduced aromaticity, which was unequivocally supported by ring‐current calculations based on the gauge‐including magnetically induced current (GIMIC) method and by calculated nucleus‐independent chemical shift (NICS) values. The negative ring current in the isocyclic E ring suggests the antiaromatic character of this moiety and also clarifies the spontaneous reactivity of the complexes with oxygen. The oxidation products were isolated and their electrochemical and photophysical properties were studied. The ruthenocene derivatives turned out to be stable under light irradiation and showed photoinduced charge transfer with charge‐separation lifetimes of 152–1029 ps.