Kent O. Kirlikovali

Luminescent metal complexes featuring photophysically innocent boron cluster ligands

We report the synthesis and characterization of a series of d8 metal complexes featuring robust and photophysically innocent strong-field chelating 1,1′-bis(o-carborane) (bc) ligand frameworks.

Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants

We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B12(OCH2Ar)12 (Ar = Ph or C6F5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized throughout the boron cluster core. Here we show how these species, photo-excited with a benchtop blue LED source, can exhibit excited-state reduction potentials as high as 3 V and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is observed in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.005 mol%. Furthermore, photo-excitation of B12(OCH2C6F5)12 in the presence of a less activated olefin such as isobutylene results in the production of highly branched poly(isobutylene). This work introduces a new class of air-stable, metal-free photo-redox reagents capable of mediating chemical transformations.

Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450–550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16–0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10–3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0–5.5 ps and then decays via recombination to the triplet or ground states in 0.9–3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11–22 ps.

Efficient energy sensitization of C60 and application to organic photovoltaics.

Fullerenes are currently the most popular electron-acceptor material used in organic photovoltaics (OPVs) due to their superior properties, such as good electron conductivity and efficient charge separation at the donor/acceptor interface. However, low absorptivity in the visible spectral region is a significant drawback of fullerenes. In this study, we have designed a zinc chlorodipyrrin derivative (ZCl) that absorbs strongly in the visible region (450-600 nm) with an optical density 7-fold higher than a C60 film. ZCl efficiently transfers absorbed photoenergy to C60 in mixed films. Application of ZCl as an energy sensitizer in OPV devices leads to an increase in the photocurrent from the acceptor layer, without changing the other device characteristics, i.e., open circuit voltage and fill factor. For example, C60-based OPVs with and without the sensitizer give 4.03 and 3.05 mA/cm(2), respectively, while both have V(OC) = 0.88 V and FF = 0.44. Our ZCl sensitization approach improves the absorbance of the electron-acceptor layer while still utilizing the beneficial characteristics of C60 in OPVs.

Multichromophoric energy sensitization of C60 for organic photovoltaics

In organic photovoltaics (OPVs), photocurrent generation is limited by absorption and exciton diffusion in the active layer. In this work, we describe the energy sensitization of C60 simultaneously by two chromophores at high volume concentrations (50%). This sensitization strategy takes advantage of the intense absorption of the sensitizers and the exceptional electron conduction and exciton diffusion length of C60 resulting in a 30% increase in photoresponse of the C60-based sensitized acceptor layer between λ = 450 nm and 670 nm and power conversion efficiency under simulated AM 1.5 G illumination. In (2,4-bis[4-(N,N-diphenylamino)-2,6-dihydroxyphenyl] squaraine)/C60 devices, sensitization results in an increase in JSC from 6.5 ± 0.2 mA/cm2 to 8.6 ± 0.2 mA/cm2 without compromising VOC or FF. These results demonstrate the robust nature of this sensitization scheme and its broad potential for application in OPVs.