Nicolle Langer

High‐Efficiency Blue and White Organic Light‐Emitting Devices Incorporating a Blue Iridium Carbene Complex

High-effi ciency white organic light-emitting devices (OLEDs) have great potential for energy saving solid-state lighting and eco-friendly fl at-display panels. [ 1 ] In addition, white OLEDs are expected to open new designs in lighting technology, such as transparent lighting panels or luminescent wallpapers because of being able to form paper-like thin fi lms. Phosphorescent OLED technology is an imperative methodology to realize higheffi ciency white OLEDs because phosphors, such as fac -tris(2phenylpyridine)iridium( III ) [Ir(ppy) 3 ] and iridium( III )bis(4,6(difl uorophenyl)pyridinatoN , C 2 ′ )picolinate (FIrpic) enable an internal effi ciency as high as 100% converting both singlet and triplet excitons into photons. [ 2 ] There are two effective approaches to obtain white OLEDs by using phosphors. One is to combine a blue fl uorophore and phosphors for the other colors, a so-called hybrid white OLED. [ 3 ] A key requirement is the use of a blue fl uorophore with higher triplet energy ( E T1 ) than that of the other phosphors. The blue fl uorophore also needs to have a high photoluminescent quantum yield ( η PL ). Schwartz and coworkers reported hybrid white OLEDs with a power effi ciency at 1000 cd m − 2 ( η p,1000 ) of 22 lm W − 1 (external quantum effi ciency (EQE) of 10.4%) by using N , N ′ -di-1-naphthalenylN , N ′ -diphenyl-[1,1 ′ :4 ′ ,1 ′ ′ :4 ′ ′ ,1 ′ ′ ′ -quaterphenyl]-4,4 ′ ′ ′ -diamine (4P-NPD) as a blue fl uorophore, and Ir(ppy) 3 and iridium( III ) bis(2-methyldibenzo-[ f , h ]quinoxaline)(acetylacetonate) [Ir(MDQ) 2 ( acac)] as green and red phosphors, respectively. [ 4 ]

Organic super-acceptors with efficient intramolecular charge-transfer interactions by [2+2] cycloadditions of TCNE, TCNQ, and F4-TCNQ to donor-substituted cyanoalkynes.

Rivaling the best one: Thermal [2+2] cycloadditions of TCNE, TCNQ, and F(4)-TCNQ to N,N-dimethylanilino-substituted cyanoalkynes afforded a new class of organic super-acceptors featuring efficient intramolecular charge-transfer interactions. These acceptors rival the acceptor F(4)-TCNQ in the propensity for reversible electron uptake as well as in electron affinity (see figure), which makes them interesting as p-type dopants for potential application in optoelectronic devices.Thermal [2+2] cycloadditions of tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)-TCNQ) to N,N-dimethylanilino-substituted (DMA-substituted) alkynes bearing either nitrile, dicyanovinyl (DCV; -CH==C(CN)(2)), or tricyanovinyl (TCV; -C(CN)==C(CN)(2)) functionalities, followed by retro-electrocyclization, afforded a new class of stable organic super-acceptors. Despite the nonplanarity of these acceptors, as revealed by X-ray crystallographic analysis and theoretical calculations, efficient intramolecular charge-transfer (CT) interactions between the DMA donors and the CN-containing acceptor moieties are established. The corresponding CT bands appear strongly bathochromically shifted with maxima up to 1120 nm (1.11 eV) accompanied by an end-absorption in the near infrared around 1600 nm (0.78 eV) for F(4)-TCNQ adducts. Electronic absorption spectra of selected acceptors were nicely reproduced by applying the spectroscopy oriented configuration interaction (SORCI) procedure. The electrochemical investigations of these acceptors by cyclic voltammetry (CV) and rotating disc voltammetry (RDV) in CH(2)Cl(2) identified their remarkable propensity for reversible electron uptake rivaling the benchmark compounds TCNQ (E(red,1)=-0.25 V in CH(2)Cl(2) vs. Fc(+)/Fc) and F(4)-TCNQ (E(red,1)=+0.16 V in CH(2)Cl(2) vs. Fc(+)/Fc). Furthermore, the electron-accepting power of these new compounds expressed as adiabatic electron affinity (EA) has been estimated by theoretical calculations and compared to the reference acceptor F(4)-TCNQ, which is used as a p-type dopant in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. A good linear correlation exists between the calculated EAs and the first reduction potentials E(red,1). Despite the substitution with strong DMA donors, the predicted EAs reach the value calculated for F(4)-TCNQ (4.96 eV) in many cases, which makes the new acceptors interesting for potential applications as dopants in organic optoelectronic devices. The first example of a charge-transfer salt between the DMA-substituted TCNQ adduct (E(red,1)=-0.27 V vs. Fc(+)/Fc) and the strong electron donor decamethylferrocene ([FeCp*(2)]; Cp*=pentamethylcyclopentadienide; E(ox,1)=-0.59 V vs. Fc(+)/Fc) is described. Interestingly, the X-ray crystal structure showed that in the solid state the TCNQ moiety in the acceptor underwent reductive sigma-dimerization upon reaction with the donor.

Donor-substituted octacyano[4]dendralenes: a new class of cyano-rich non-planar organic acceptors

Double [2+2] cycloaddition/retro-electrocyclisation reactions between tetracyanoethene (TCNE) and various anilino-capped buta-1,3-diynes furnished a series of octacyano[4]dendralene derivatives featuring intense, low-energy intramolecular charge-transfer absorptions. These novel chromophores are strong electron acceptors and undergo facile one-electron reductions at potentials (–0.09 to –0.17 eV vs.Fc+/Fc, in CH2Cl2–0.1 M nBu4NPF6) lower than those reported for the benchmark organic acceptors, such as TCNE (–0.32 eV) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) (–0.25 eV). The electron-accepting power of one octacyano[4]dendralene, as expressed by the computed adiabatic electron affinity (EA), compares to that of the reference acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) used as a p-type dopant in organic light-emitting diodes (OLEDs) and solar cells. Gas-phase density functional theory (DFT) calculations predict a stretched-out conformation as the global energy minimum for octacyano[4]dendralenes. In the solid state however, folded conformations were observed for two structures by X-ray analysis. Taking the solid state environment approximately into account calculations predict a energetical degeneracy between the stretched-out and folded conformation. Therefore conformational preference probably is a result of supramolecular dimer formation, mediated by two pairs of intermolecular, antiparallel dipolar CN⋯CN interactions.