Synthesis and characterization of a hydrophilic conjugated 4+4 Re(I)-porphyrin metallacycle

• Published in: Inorganica Chimica Acta Vol. 453; pp. 376 - 384
• Main Authors: Milano, Domenico, Đorđević, Luka, Zangrando, Ennio, Iengo, Elisabetta, Tecilla, Paolo
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.11.2016; Elsevier Science Ltd
• Subjects: Chemical synthesis; Ligands; Metal mediated self-assembling; Metallacycle; Mica; Nanostructured materials; NMR; Nuclear magnetic resonance; Organometallic compounds; Polyoxyethylene; Re(I); Spray deposition; Structural analysis; Substrates; trans-di(4-pyridyl)porphyrin; Metallacycle; Metal mediated self-assembling; trans-di(4-pyridyl)porphyrin; Re(I)
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2016.08.039

The synthesis and the full NMR characterization, including VT 1H DOSY-NMR experiments and the 13C-NMR spectrum, of a new 4+4 Re(I)-porphyrin metallacycle is described. When sprayed on a heated mica substrate the metallacycle forms regular ring-like nano-structures which are not formed by the parent porphyrin. [Display omitted] •A trans-dipyridylporphyrin bearing two short polyoxyethylene chains has been prepared.•Reaction of the porphyrin with a Re(I) complex forms a 4+4 metallacycle soluble in common organic solvents.•The metallacycle has been fully characterized by NMR including 13C-NMR and VT 1H DOSY-NMR experiments.•Spray deposition of the metallacycle on mica led to the formation of regular ring-like nano-structures. The preparation and the full characterization, including the X-ray structure determination, of a polar trans-dipyridylporphyrin functionalized with two short polyoxyethylene chains is reported. Reaction of the porphyrin with a Re(I) complex yielded a 4+4 metallacycle showing an improved solubility and a lower tendency to aggregate with respect to analogous porphyrin cyclic derivatives. These properties allowed a full NMR characterization of the metallacycle including VT 1H DOSY-NMR experiments and, for the first time, the recording of a 13C-NMR spectrum giving further insight into the structural definition of these type of metallacycles. Spray deposition of the metallacycle on a heated mica substrate shows the formation of regular ring-like nano-structures which are not formed by the parent porphyrin.