Reactivity of Nickel(II) Porphyrins in oCVD Processes-Polymerisation, Intramolecular Cyclisation and Chlorination.
Giuseppe BengasiKamal BabaOliver BackGilles FracheKatja HeinzeNicolas D BoscherPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2019)
Oxidative chemical vapour deposition of (5,15-diphenylporphyrinato)nickel(II) (NiDPP) with iron(III) chloride as oxidant yielded a conjugated poly(metalloporphyrin) as a highly coloured thin film, which is potentially useful for optoelectronic applications. This study clarified the reactive sites of the porphyrin monomer NiDPP by HRMS, UV/Vis/NIR spectroscopy, cyclic voltammetry and EPR spectroscopy in combination with quantum chemical calculations. Unsubstituted meso positions are essential for successful polymerisation, as demonstrated by varying the porphyrin meso substituent pattern from di- to tri- and tetraphenyl substitution. DFT calculations support the proposed radical oxidative coupling mechanism and explain the regioselectivity of the C-C coupling processes. Depositing the conjugated polymer on glass slides and on thermoplastic transparent polyethylene naphthalate demonstrated the suitability of the porphyrin material for flexible optoelectronic devices.
Keyphrases
- photodynamic therapy
- density functional theory
- molecular dynamics
- metal organic framework
- energy transfer
- fluorescence imaging
- single molecule
- high resolution
- solid state
- electron transfer
- molecular dynamics simulations
- monte carlo
- room temperature
- drinking water
- molecular docking
- high resolution mass spectrometry
- biofilm formation
- escherichia coli
- drug release
- pseudomonas aeruginosa
- ionic liquid
- simultaneous determination