ABSTRACT
A series of square planar metalloporphyrins (M(TPP), TPP is 5,10,15,20-tetraphenylporphyrin and M(TPFPP), TPFPP is 5,10,15,20-tetrapentafluorophenylporphyrin; M is Zn2+, Ni2+, Pd2+, or Pt2+) with distinct meso-substituents were prepared, and their magneto-optical activity (MOA) was characterized by magnetic circular dichroism (MCD) and magneto-optical rotary dispersion spectroscopy (MORD; also known as Faraday rotation spectroscopy). MOA is crucial in the development of next-generation magneto-optical devices and quantum computing. The data show that the presence of meso-pentafluorophenyl substituents results in significant increase in MOA in comparison to the homologous phenyl group. Differences in the MOA of these metalloporphyrins are rationalized using the Gouterman four-orbital model and pave the way for rational design of improved and tailorable magneto-optical materials.
ABSTRACT
We have prepared a series of complexes of the type [IrIII(ppy)2(L]n+ complexes (1-4), where ppy is a substituted 2-phenylpyridine and L is a chelating phosphine thioether ligand. The parent complex (1) comprises an unsubstituted phenylpyridine ligand, whereas complex 2 contains a nitro substituent on the pyridine ring, complex 3 features a diphenylamine group on the phenyl ring, and 4 has both nitro and diphenylamine groups. Crystallographic, 1H NMR, and elemental analysis data are consistent with each of the chemical formulae. DFT (density functional theory) computational results show a complicated electronic structure with contributions from Ir, ppy, and the PS ligand. Ultrafast pump-probe data show strong contributions from the phenylpyridine moieties as well as strong panchromatic excited state absorption transitions. The data show that nitro and/or diphenylamine substituents dominate the spectroscopy of this series of compounds.
ABSTRACT
In this work, our group synthesized and characterized a fully conjugated graft polymer comprising of a donor-acceptor molecular backbone and regioregular poly(3-hexylthiophene) (RRP3HT) side chains. Here, our macromonomer (MM) was synthesized via Kumada catalyst transfer polycondensation reaction based on ditin-benzodithiophene (BDT) initiator. The tin content of MM was then investigated by inductively coupled plasma-mass spectrometry (ICP-MS), which allowed for accurate control of donor/acceptor monomer ratio of 1:1 for the following Stille coupling polymerization toward our graft polymer (BP). The structures of the polymers were then characterized by gel permeation chromatography (GPC), NMR, and elemental analysis. This was followed by the characterization of optical, electrochemical, and physical properties. The magneto-optical activity of graft polymer BP was then measured. It was found that, despite the presence of the acceptor backbone, the characteristic large Faraday rotation of RRP3HT was maintained in polymer BP, which exhibited a Verdet constant of 2.39 ± 0.57 (104) °/T·m.
