Initiated by excited-state intramolecular proton transfer (ESIPT) reaction, an overall reaction cycle of 4-(2-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (o-HBDI), an analogue of the core chromophore of the green fluorescent protein (GFP), has been investigated. In contrast to the native GFP core, 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (p-HBDI), which requires hydrogen-bonding relay to accomplish proton transfer in vivo, o-HBDI possesses a seven-membered-ring intramolecular hydrogen bond and thus provides an ideal system for mimicking an intrinsic proton-transfer reaction. Upon excitation, ESIPT takes place in o-HBDI, resulting in a ∼600 nm proton-transfer tautomer emission. The o-HBDI tautomer emission, resolved by fluorescence upconversion, is comprised of an instantaneous rise to a few hundred femtosecond oscillation in the early relaxation stage. Frequency analysis derived from ultrashort pulse gives two low-frequency vibrations at 115 and 236 cm(-1), corresponding to skeletal deformation motions associated with the hydrogen bond. The results further conclude that ESIPT in o-HBDI is essentially triggered by low-frequency motions and may be barrierless along the reaction coordinate. Femtosecond UV/vis transient absorption spectra also provide supplementary evidence for the structural evolution during the reaction. In CH(3)CN, an instant rise of a 530 nm transient is resolved, which then undergoes 7.8 ps decay, accompanied by the growth of a rather long-lived 580 nm transient species. It is thus concluded that following ESIPT the cis-proton transfer isomer undergoes cis-trans-isomerization. The results of viscosity-dependent dynamics are in favor of the one-bond-flip mechanism, which is in contrast to the volume-conserving isomerization behavior for cis-stilbene and p-HBDI. Further confirmation is given by the picosecond-femtosecond transient IR absorption spectra, where several new and long-lived IR bands in the range of 1400-1500 cm(-1) are assigned to the phenyl in-plane breathing motions of the trans-proton transfer tautomer. Monitored by the nanosecond transient absorption, the 580 nm transient undergoes a ∼7.7 μs decay constant, accompanied by the growth of a new ∼500 nm band. The latter is assigned to a deprotonated tautomer species, which then undergoes the ground-state reverse proton recombination to the original o-HBDI in ∼50 μs, achieving an overall, reversible proton transfer cycle. This assignment is unambiguously supported by pump-probe laser induced fluorescence studies. On these standpoints, a comparison of photophysical properties among o-HBDI, p-HBDI, and wild-type GFP is discussed in detail.

We report the design strategy and synthesis of a structurally locked GFP core chromophore p-LHBDI, its ortho-derivative, o-LHBDI, and H2BDI possessing both para- and ortho-hydroxyl groups such that the inherent rotational motion of the titled compounds has been partially restricted. o-LHBDI possesses a doubly locked configuration, i.e., the seven-membered ring hydrogen bond and five-membered ring C(4-5-10-13-14) cyclization, from which the excited-state intramolecular proton transfer takes place, rendering a record high tautomer emission yield (0.18 in toluene) and the generation of amplified spontaneous emission. Compared with their unlocked counterparts, a substantial increase in the emission yield is also observed for p-LHBDI and H2BDI in anionic forms in water, and accordingly the structure versus luminescence relationship is fully discussed based on their chemistry and spectroscopy aspect. In solid, o-LHBDI exhibits an H-aggregate-like molecular packing, offers narrow-bandwidth emission, and has been successfully applied to fabricate a yellow organic light emitting diodes (λmax = 568 nm, ηext = 1.9%) with an emission full width at half-maximum as narrow as 70 nm.

o-Hydroxy analogues, 1a-g, of the green fluorescent protein chromophore have been synthesized. Their structures and electronic properties were investigated by X-ray single-crystal analyses, electrochemistry, and luminescence properties. In solid and nonpolar solvents 1a-g exist mainly as Z conformers that possess a seven-membered-ring hydrogen bond and undergo excited-state intramolecular proton transfer (ESIPT) reactions, resulting in a proton-transfer tautomer emission. Fluorescence upconversion dynamics have revealed a coherent type of ESIPT, followed by a fast vibrational/solvent relaxation (<1 ps) to a twisted (regarding exo-C(5)-C(4)-C(3) bonds) conformation, from which a fast population decay of a few to several tens of picoseconds was resolved in cyclohexane. Accordingly, the proton-transfer tautomer emission intensity is moderate (0.08 in 1e) to weak (∼10(-4) in 1a) in cyclohexane. The stronger intramolecular hydrogen bonding in 1g suppresses the rotation of the aryl-alkene bond, resulting in a high yield of tautomer emission (Φ(f) ≈ 0.2). In the solid state, due to the inhibition of exo-C(5)-C(4)-C(3) rotation, intense tautomer emission with a quantum yield of 0.1-0.9 was obtained for 1a-g. Depending on the electronic donor or acceptor strength of the substituent in either the HOMO or LUMO site, a broad tuning range of the emission from 560 (1g) to 670 nm (1a) has been achieved.

The experimental demonstrations of light-emitting diode (LED) fabrication with surface plasmon (SP) coupling with the radiating dipoles in its quantum wells are first reviewed. The SP coupling with a radiating dipole can create an alternative emission channel through SP radiation for enhancing the effective internal quantum efficiency when the intrinsic non-radiative recombination rate is high, reducing the external quantum efficiency droop effect at high current injection levels, and producing partially polarized LED output by inducing polarization-sensitive SP for coupling. Then, we report the theoretical and numerical study results of SP-dipole coupling based on a simple coupling model between a radiating dipole and the SP induced on a nearby Ag nanoparticle (NP). To include the dipole strength variation effect caused by the field distribution built in the coupling system (the feedback effect), the radiating dipole is represented by a saturable two-level system. The spectral and dipole-NP distance dependencies of dipole strength variation and total radiated power enhancement of the coupling system are demonstrated and interpreted. The results show that the dipole-SP coupling can enhance the total radiated power. The enhancement is particularly effective when the feedback effect is included and hence the dipole strength is increased.

A systematic study on the effects of heteroarenes on the solid state structure and optoelectronic properties of isoindigo analogues, namely, PBDT-IIG and PBDT-TIIG, used in solution-processed organic field effect transistors (OFETs) and organic photovoltaics (OPVs) is reported. We discover that the optical absorption, frontier orbitals, backbone coplanarity, molecular orientation, solubility, film morphology, charge carrier mobility, and solar cell performance are critically influenced by the heteroarenes in the acceptor subunits. PBDT-IIG exhibits good p-type OFET performance with mobility up to 1.03 × 10–1 cm2 V–1 s–1, whereas PBDT-TIIG displays ambipolar mobilities of μh = 7.06 × 10–2 cm2 V–1 s–1 and μe = 2.81 × 10–4 cm2 V–1 s–1. PBDT-IIG and PBDT-TIIG blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) yield promising power conversion efficiencies (PCEs) of 5.86% and 2.55%, respectively. The excellent mobility of PBDT-IIG can be attributable to the growing fraction of edge-on packing by the interfacial surface treatment. Although PBDT-TIIG could construct a long-range face-on packing alignment to meliorate its photocurrent in OPV applications, the low open-circuit voltage caused by its high-lying HOMO energy level and greater recombination demonstrates the trade-off between light absorption and solar cell performance. Nevertheless, PBDT-TIIG with a PCE of 2.55% is the highest reported PCE to date for the TIIG-based systems.