MCD and MCPL Characterization of Luminescent Si(IV) and P(V) Tritolylcorroles: The Role of Coordination Number

Abstract

Two triarylcorrole complexes, (hydroxy) [5,10,15tritolylcorrolato]silicon-(TTC)Si(OH) and (dihydroxy) [5,10,15tritolylcorrolato]phosphorous-(TTC)P(OH) 2 , have been investigated by magnetic circular dichroism (MCD) and magnetic circularly polarized luminescence (MCPL). The spectroscopic investigations have been combined with explicit calculation of MCD response through time-dependent density functional theory (TD-DFT) formalism. This has allowed us to better define the role of molecular orbitals in the transitions associated with the Soret and Q bands. Besides and more importantly, MCD has made it possible to follow the titration process of (TTC)Si(OH) in dimethyl sulfoxide (DMSO) solution with NaF and of (TTC)P(OH) 2 in dichloromethane solution with alcohols in a complementary and, we dare say, more sensitive way with respect to absorption and fluorescence data. Finally, the MCPL spectra and the ancillary TD-DFT calculations have allowed us to characterize the excited state of (TTC)Si(OH).

Magnetic Circularly Polarized Luminescence of Organic Compounds

“…Note that in the case of ZnOEP and TTDPzM , even though metals ions are present, the spectroscopic features discussed here are entirely determined by the organic porphyrin cores. Finally, the same group studied the MCPL associated with the Q band of a Si‐corrole compound, [24] (TTC)Si(OH) (Scheme 1). (TTC)Si(OH) showed a positive MCPL band, opposed to the ones observed for porphyrins, around 580 nm with a g MCPL of the order of 10 −3 T −1 .…”

Enhancement of circularly polarized electroluminescence via reflection reversal under a magnetic field

“…In recent years, external static magnetic fields have garnered significant attention as a physical bias to induce circularly polarised signals in the photoexcited states of achiral and racemic organic, organic-inorganic, or inorganic luminescent materials. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] In this context, we have succeeded in generating full-colour red-green-blue-yellow (RGBY) CPEL under a magnetic field from organic light-emitting diodes (OLEDs) incorporated with optically inactive phosphorescent iridium(III) luminophores in the EML. That is, the application of an external magnetic field allows us to develop phosphorescent CP-OLEDs without any chiral phosphors, namely, magnetic CP-OLED (MCP-OLEDs).…”

External Magnetic Field Driven, Ambidextrous Circularly Polarized Electroluminescence from Organic Light Emitting Diodes Containing Racemic Cyclometalated Iridium(III) Complexes

“…[38][39][40][41] An external static magnetic (EMF) field is now established as a versatile physical bias that induces chiroptical spectral signals in the ground and photoexcited states of several achiral and racemic organic, and organometallic emitters. [42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] It is well known that chiral Ir(III) complexes exhibit CPL. [57][58][59][60][61] We have recently reported MCPL from racemic mixtures of fac-tris-cyclometalated Ir(III)(ppy) 3 and bis-cyclometalated Ir(III)(ppy) 2 (acac) (ppy: 2-phenylpyridinate, acac: acetylacetonate), as phosphorescence emitters, under 1.6 T EMF at room temperature (Figure 1).…”

“…The magnetic circularly polarized luminescence (MCPL) theory by Riehl and Richardson [37] prompted several experiments using symmetric, achiral, and racemic mixtures of lanthanide complexes with achiral ligands, under one of two possible Faraday geometries [38–41] . An external static magnetic (EMF) field is now established as a versatile physical bias that induces chiroptical spectral signals in the ground and photoexcited states of several achiral and racemic organic, and organometallic emitters [42–56] …”