Ying-Li Rao

Reversible Intramolecular C−C Bond Formation/Breaking and Color Switching Mediated by a N,C-Chelate in (2-ph-py)BMes2 and (5-BMes2-2-ph-py)BMes2

A diboron compound with both 3-coordinate boron and 4-coordinate boron centers, (5-BMes2-2-ph-py)BMes2 (1) and its monoboron analogue, (2-ph-py)BMes2 (2) have been synthesized. Both compounds are luminescent but have a high sensitivity toward light. UV and ambient light cause both compounds to isomerize to 1a and 2a, respectively, via the formation of a C-C bond between a mesityl and the phenyl group, accompanied by a drastic color change from yellow or colorless to dark olive green or dark blue. The structures of 1a and 2a were established by 2D NMR experiments and geometry optimization by DFT calculations. Both 1a and 2a can thermally reverse back to 1 and 2 via the breaking of a C-C bond, with the activation barrier being 107 and 110 kJ/mol, respectively. The N,C-chelate ligands in 1 and 2 were found to play a key role in promoting this unusual and reversible photo-thermal isomerization process on a tetrahedral boron center. Reactions with oxygen molecules convert 1a and 2a to 5-BMes2-2-[(2-Mes)-ph]-pyridine (1b) and 2-(2-Mes)-ph-pyridine (2b), respectively.

Highly efficient blue phosphorescent and electroluminescent Ir(III) compounds

Three new Ir(III) compounds with deep-blue phosphorescence have been synthesized. These molecules have the general formula of Ir(C∧N)2(L∧X), where C∧N = 2′,6′-difluoro-2,3′-bipyridine (dfpypy) and L∧X = ancillary ligand such as 2-picolinate, pic (1), acetylacetonate, acac (2), or dipivaloylmethanoate, dpm (3). The ancillary ligands have been found to significantly destabilize both HOMO and LUMO levels of the Ir(III) complexes, compared to Ir(dfpypy)3, without significantly changing the phosphorescence energy. Compounds 1–3 emit bright blue phosphorescence with λmax = 440–460 nm and quantum efficiencies of 0.60–0.95 in solution and the solid state. Double-layer electroluminescent devices using compounds 1–3 as the dopant, CDBP (4,4′-bis(9-carbazolyl)-2,2′-dimethylbiphenyl) as the host/hole transporting layer, and TPBi (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene) as the electron transport layer have been fabricated. These EL devices show pure blue colour with high efficiency. The EL device of compound 3 at the doping level of 20 wt% shows the best performance with EQE of 10–15% at the brightness of 10–1000 cd m−2 and the maximum current efficiency of 22 cd A−1.

Stepwise Intramolecular Photoisomerization of NHC-Chelate Dimesitylboron Compounds with C–C Bond Formation and C–H Bond Insertion

C,C-chelate dimesitylboron (BMes(2)) compounds containing an N-heterocyclic carbene (NHC) donor have been obtained. Single-crystal X-ray diffraction analyses established that the boron atom in these compounds is bound by four carbon atoms in a distorted tetrahedral geometry. Compared to previously reported N,C-chelate dimesitylboron compounds, the new C,C-chelate boron compounds have a much larger HOMO-LUMO energy gap (>3.60 eV). They do, however, respond to UV irradiation (300 nm) in the same manner as N,C-chelate BMes(2) compounds do, undergoing photoisomerization and converting to an intensely colored (yellow or orange) isomer A quantitatively, with a high quantum efficiency (0.60-0.75). NMR and single-crystal X-ray diffraction analyses established that the structure of A is similar to the dark isomers obtained from N,C-chelate BMes(2) compounds. However, unlike the N,C-chelate dark isomers that have the tendency to thermally reverse back to the light colored isomers, the isomers A of the C,C-chelate BMes(2) are thermally stable and no reverse isomerization was observed even when heated to 80 °C (or 110 °C) for hours. The most unusual finding is that isomers A undergo further photoisomerization when irradiated at 350 nm, forming a new colorless species B nearly quantitatively. NMR and single-crystal X-ray diffraction analyses established the structure of isomer B, which may be considered as an intramolecular C-H insertion product via a borylene intermediate. Mechanistic aspects of this unusual two-step photoisomerization process have been examined by DFT computational studies.

Photo- and Thermal-Induced Multistructural Transformation of 2-Phenylazolyl Chelate Boron Compounds

The new N,C-chelate boron compounds B(2-phenylazolyl)Mes2 [Mes = mesityl; azolyl = benzothiazolyl (1a), 4-methylthiazolyl (2a), benzoxazolyl (3a), benzimidazolyl (4a)] undergo an unprecedented multistructural transformation upon light irradiation or heating, sequentially producing isomers b, c, d, and e. The dark isomers b generated by photoisomerization of a undergo a rare thermal intramolecular H-atom transfer (HAT), reducing the azole ring and generating new isomers c, which are further transformed into isomers d. Remarkably, isomers d can be converted to their diastereomers e quantitatively by heating, and e can be converted back to d by irradiation at 300 nm. The structures of isomers 1d and 1e were established by X-ray diffraction. The unusual HAT reactivity can be attributed to the geometry of the highly energetic isomers b and the relatively low aromaticity of the azole rings. The boryl unit plays a key role in the reversible interconversion of d and e, as shown by mechanistic pathways established through DFT and TD-DFT calculations.

Exciton-stimulated molecular transformation in organic light-emitting diodes.

An exciton-stimulated molecular transformation in an organic light-emitting diode (OLED) on a time scale of a few seconds under electrical bias is shown to reach nearly 100% under standard operating conditions, leading to color switching. It is reversible in both a thin film and an OLED when sufficient thermal energy is supplied. Such an exciton-stimulated molecular transformation suggests a new process which may be exploited for applications such as electrochromic and memory devices.

Tuning the Colors of the Dark Isomers of Photochromic Boron Compounds with Fluoride Ions: Four-State Color Switching.

Combining a three-coordinated boron (BMes2) moiety with a four-coordinated photochromic organoboron unit leads to a series of new diboron compounds that undergo four-state reversible color switching in response to stimuli of light, heat, and fluoride ions. Thus, these hybrid diboron systems allow both convenient color tuning/switching of such photochromic systems, as well as visual fluoride sensing by color or fluorescent emission color change.