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•The novel amphiphilic AIEgen copolymers based and NIPAM and tetraphenylethylene (TPE) for fluorescence sensor were fabricated.•Multi-stimuli responsive fluorescence of AIE copolymers ...were investigated under various external stimuli (at different temperatures and acid/base conditions).•Ultrafast, remarkably sensitive and selective Cu2+ detection in aqueous media and test strips were achieved based on the TPE fluorescence quenching via photoinduced electron transfer (PET) phenomena.•Owing to good water solubilities, amphiphilic copolymers P1 and P2 (containing only 1.6 and 0.6 % molar ratios of AIEgen) exhibit significant sensing towards Cu2+ with very prominent limit of detection values (LOD = 57 and 72 nM, respectively)
Novel multi-stimuli responsive fluorescence sensors based on amphiphilic copolymers containing hydrophilic N-isopropylmethacrylamide (NIPAM) and AIEgenic tetraphenylethylene-dipicolylamine (TPEDPA) monomers attached to side-chains of copolymers are synthesized. Two copolymers poly(NIPAM)x-co-(TPEDPA)y prepared by free radical polymerization with different molar ratios of monomers NIPAM and TPEDPA (i.e., x:y = 60:1 and 175:1 for P1 and P2, respectively) show good solubilities in organic solvents and water, which exhibit strong cyan fluorescence at 466 nm in aggregation and solid states due to AIE behaviors of TPE units. Upon various external stimuli (temperatures and acid/base conditions), P1 and P2 possess excellent reversible thermo- and pH-responsive fluorescence turn-off/on cyan emissions of TPE units. In addition, with DPA receptor, P1 and P2 are applied as ultrafast, selective and sensitive fluorescence probes for copper ion detection in water based on the TPE fluorescence quenching via photoinduced electron transfer (PET) phenomena, which can be recovered by the addition of disodium ethylenediaminetetraacetate solution. Owing to good water solubilities, amphiphilic copolymers P1 and P2 (containing only 1.6 and 0.6 % molar ratios of AIEgen) exhibit significant sensing towards Cu2+ with very prominent limit of detection values (LOD = 57 and 72 nM, respectively), which are much better than that of hydrophobic monomer TPEDPA (590 nM). Moreover, the fluorescence quenching of TPE units due to PET phenomena is further confirmed by theoretical calculations. Additionally, as an excellent quenching fluorescence sensor with good biocompatibility of P1, its recognition of copper ion and bio-imaging applications in living cells are also reported in this research.
Pentalenes are formally eight-π-electron antiaromatic, but π-expanded pentalenes can display varying levels of paratropicity depending on the choice of annelated (hetero)arenes and the geometry of ...π-expansion (i.e., linear vs bent topologies) around the 4n core. Here, we explain the effects of annelation on the paratropicity of π-expanded pentalenes by relating the electronic structure of pentalenes to a pair of conjoined pentafulvenes.
A series of novel photo-switchable 2rotaxanes (i.e.,
Rot-A-SP
and
Rot-B-SP
before and after shuttling controlled by acid–base, respectively) containing one spiropyran (SP) unit (as a photochromic ...stopper) on the axle and two tetraphenylethylene (TPE) units on the macrocycle were synthesized via click reaction. Upon UV/visible light exposure, both mono-fluorophoric rotaxanes
Rot-A-SP
and
Rot-B-SP
with the closed form (i.e., non-emissive SP unit) could be transformed into the open form (i.e., red-emissive merocyanine (MC) unit) to acquire their respective bi-fluorophoric
Rot-A-MC
and
Rot-B-MC
reversibly. The aggregation-induced emission (AIE) properties of bi-fluorophoric TPE combined with MC AIEgens of these designed rotaxanes and mixtures in semi-aqueous solutions induced interesting ratiometric photoluminescence (PL) and Förster resonance energy transfer (FRET) behaviors, which were further investigated and verified by dynamic light scattering (DLS), X-ray diffraction (XRD), and time-resolved photoluminescence (TRPL) measurements along with theoretical studies. Accordingly, in contrast to the model axle (
Axle-MC
) and the analogous mixture (
Mixture-MC
, containing the axle and macrocycle components in a 1:1 molar ratio), more efficient FRET behaviors and stronger red PL emissions were obtained from dual-AIEgens between a blue-emissive TPE donor (PL emission at 468 nm) and a red-emissive MC acceptor (PL emission at 668 nm) in both novel photo-switchable 2rotaxanes
Rot-A-MC
and
Rot-B-MC
under various external modulations, including water content, UV/Vis irradiation, pH value, and temperature. Furthermore, the reversible fluorescent photo-patterning applications of
Rot-A-SP
in a powder form and a solid film with excellent photochromic and fluorescent behaviors are first investigated in this report.
A novel amphiphilic aggregation-induced emission (AIE) copolymer, that is, poly(NIPAM-co-TPE-SP), consisting of N-isopropylacrylamide (NIPAM) as a hydrophilic unit and a ...tetraphenylethylene–spiropyran monomer (TPE-SP) as a bifluorophoric unit is reported. Upon UV exposure, the close form of non-emissive spiropyran (SP) in poly(NIPAM-co-TPE-SP) can be photo-switched to the open form of emissive merocyanine (MC) in poly(NIPAM-co-TPE-MC) in an aqueous solution, leading to ratiometric fluorescence of AIEgens between green TPE and red MC emissions at 517 and 627 nm, respectively, via Förster resonance energy transfer (FRET). Distinct FRET processes of poly(NIPAM-co-TPE-MC) can be observed under various UV and visible light irradiations, acid–base conditions, thermal treatments, and cyanide ion interactions, which are also confirmed by theoretical studies. The subtle perturbations of environmental factors, such as UV exposure, pH value, temperature, and cyanide ion, can be detected in aqueous media by distinct ratiometric fluorescence changes of the FRET behavior in the amphiphilic poly(NIPAM-co-TPE-MC). Moreover, the first FRET sensor polymer poly(NIPAM-co-TPE-MC) based on dual AIEgens of TPE and MC units is developed to show a very high selectivity and sensitivity with a low detection limit (LOD = 0.26 μM) toward the cyanide ion in water, which only contain an approximately 1% molar ratio of the bifluorophoric content and can be utilized in cellular bioimaging applications for cyanide detections.
Novel aggregation-induced emission (AIE) polymers, i.e., P1-SP and P2-SP, consisting of AIEgenic tetraphenylethylene (TPE) and photochromic spiropyran (SP) units are reported. Both P1-SP and P2-SP ...exhibit excellent AIE behaviours of TPE moieties in near-aqueous solutions THF/H2O (95% water) and solid states with strong cyan and blue emissions at 494 and 477 nm, respectively. Upon acidification, the close forms of P1-SP and P2-SP can be opened and switched to open P1-MCH+ and P2-MCH+ structures of protonated merocyanine (MCH+), resulting in fluorescence quenching of TPE units through corresponding intramolecular charge transfer (ICT) and Förster resonance energy transfer (FRET) processes. The fluorescence recovery of TPE can be monitored by the neutralization of P1-MCH+ and P2-MCH+ with base solutions under ambient/visible light attributed to the re-close P1-SP and P2-SP structures, which led to respective turn-off ICT and FRET phenomena. Distinct fluorescence quenching behaviours of P1-SP and P2-SP can be observed under various stimuli, including acid conditions and ferric ion interactions, which are also confirmed by theoretical studies. Moreover, P1-SP and P2-SP can be utilized as fluorescence quenching sensors for nanomolar level detections of ferric ion (LOD = 166 and 110 nM for corresponding P1-SP and P2-SP) with excellent selectivities in near-aqueous solutions and paper test strips. Additionally, the interesting visible and fluorescence colour changes of coated cellulosic papers, blended PMMA films and powder forms based on P1-SP and P2-SP under multi-external stimuli (acid-base vapour and visible light/heating processes) are also explored in this report.
We introduce phosphorescent platinum aryl acetylide complexes supported by tert-butyl-isocyanide and strongly σ-donating acyclic diaminocarbene (ADC) ligands. The precursor complexes ...cis-Pt(CNtBu)2(CCAr)2 (4a–4f) are treated with diethylamine, which undergoes nucleophilic addition with one of the isocyanides to form the cis-Pt(CNtBu)(ADC)(CCAr)2 complexes (5a–5f). The new compounds incorporate either electron-donating groups (4-OMe and 4-NMe2) or electron-withdrawing groups 3,5-(OMe)2, 3,5-(CF3)2, 4-CN, and 4-NO2 on the aryl acetylide. Experimental HOMO–LUMO gaps, estimated from cyclic voltammetry, span the range of 2.68–3.61 eV and are in most cases smaller than the unsubstituted parent complex, as corroborated by DFT. In the ADC complexes, peak photoluminescence wavelengths span the range of 428 nm (2a, unsubstituted phenylacetylide) to 525 nm (5f, 4-NO2-substituted), with the substituents inducing a red shift in all cases. The phosphorescence E 0,0 values and electrochemical HOMO–LUMO gaps are loosely correlated, showing that both can be reduced by either electron-donating or electron-withdrawing substituents on the aryl acetylides. The photoluminescence quantum yields in the ADC complexes are between 0.044 and 0.31 and the lifetimes are between 4.8 and 14 μs, a factor of 1.8–10× higher (for ΦPL) and 1.2–3.6× longer (for τ) than the respective isocyanide precursor (ΦPL = 0.014–0.12, τ = 2.8–8.2 μs).
Van der Waals (vdW) heterostructures of 2D atomically thin layered materials (2DLMs) provide a unique platform for constructing optoelectronic devices by staking 2D atomic sheets with unprecedented ...functionality and performance. A particular advantage of these vdW heterostructures is the energy band engineering of 2DLMs to achieve interlayer excitons through type‐II band alignment, enabling spectral range exceeding the cutoff wavelengths of the individual atomic sheets in the 2DLM. Herein, the high performance of GaTe/InSe vdW heterostructures device is reported. Unexpectedly, this GaTe/InSe vdWs p–n junction exhibits extraordinary detectivity in a new shortwave infrared (SWIR) spectrum, which is forbidden by the respective bandgap limits for the constituent GaTe (bandgap of ≈1.70 eV in both the bulk and monolayer) and InSe (bandgap of ≈1.20–1.80 eV depending on thickness reduction from bulk to monolayer). Specifically, the uncooled SWIR detectivity is up to ≈1014 Jones at 1064 nm and ≈1012 Jones at 1550 nm, respectively. This result indicates that the 2DLM vdW heterostructures with type‐II band alignment produce an interlayer exciton transition, and this advantage can offer a viable strategy for devising high‐performance optoelectronics in SWIR or even longer wavelengths beyond the individual limitations of the bandgaps and heteroepitaxy of the constituent atomic layers.
GaTe/InSe van der Waals heterostructure photodetectors present an extraordinary detectivity D* (1014–1012 Jones) in a shortwave infrared spectrum of 1.0−1.55 µm forbidden by the bandgap limits of the constituent GaTe and InSe, which is attributed to the formation of the interlayer transition in the type‐II band alignment heterostructure.
Dielectric properties of ultrathin Al2O3 (1.1–4.4 nm) in metal–insulator–metal (M–I–M) Al/Al2O3/Al trilayers fabricated in situ using an integrated sputtering and atomic layer deposition (ALD) system ...were investigated. An M–I interfacial layer (IL) formed during the pre-ALD sample transfer even under high vacuum has a profound effect on the dielectric properties of the Al2O3 with a significantly reduced dielectric constant (εr) of 0.5–3.3 as compared to the bulk εr ∼ 9.2. Moreover, the observed soft-type electric breakdown suggests defects in both the M–I interface and the Al2O3 film. By controlling the pre-ALD exposure to reduce the IL to a negligible level, a high εr up to 8.9 was obtained on the ALD Al2O3 films with thicknesses from 3.3 to 4.4 nm, corresponding to an effective oxide thickness (EOT) of ∼1.4–1.9 nm, respectively, which are comparable to the EOTs found in high-K dielectrics like HfO2 at 3–4 nm in thickness and further suggest that the ultrathin ALD Al2O3 produced in optimal conditions may provide a low-cost alternative gate dielectric for CMOS. While εr decreases at a smaller Al2O3 thickness, the hard-type dielectric breakdown at 32 MV/cm and in situ scanning tunneling spectroscopy revealed band gap ∼2.63 eV comparable to that of an epitaxial Al2O3 film. This suggests that the IL is unlikely a dominant reason for the reduced εr at the Al2O3 thickness of 1.1–2.2 nm but rather a consequence of the electron tunneling as confirmed in the transport measurement. This result demonstrates the critical importance in controlling the IL to achieving high-performance ultrathin dielectric in MIM structures.
Despite a growing understanding of factors that drive monomer self-assembly to form supramolecular polymers, the effects of aromaticity gain have been largely ignored. Herein, we document the ...aromaticity gain in two different self-assembly modes of squaramide-based bolaamphiphiles. Importantly, O → S substitution in squaramide synthons resulted in supramolecular polymers with increased fiber flexibility and lower degrees of polymerization. Computations and spectroscopic experiments suggest that the oxo- and thiosquaramide bolaamphiphiles self-assemble into “head-to-tail” versus “stacked” arrangements, respectively. Computed energetic and magnetic criteria of aromaticity reveal that both modes of self-assembly increase the aromatic character of the squaramide synthons, giving rise to stronger intermolecular interactions in the resultant supramolecular polymer structures. These examples suggest that both hydrogen-bonding and stacking interactions can result in increased aromaticity upon self-assembly, highlighting its relevance in monomer design.
Cyclometalated iridium complexes have emerged as top-performing emitters in organic light-emitting diodes (OLEDs) and other optoelectronic devices. A persistent challenge has been the development of ...cyclometalated iridium complexes with deep blue luminescence that have the requisite color purity, efficiency, and stability to function in color displays. In this work we report a new class of cyclometalated iridium complexes with saturated blue luminescence. These complexes have the general structure Ir(C^C:
NHC
)
2
(C^C:
ADC
), where C^C:
NHC
is an N-heterocyclic carbene (NHC) derived cyclometalating ligand and C^C:
ADC
is a different type of cyclometalating ligand featuring an acyclic diaminocarbene (ADC). The complexes are prepared by a cascade reaction that involves nucleophilic addition of propylamine to an isocyanide precursor followed by base-assisted cyclometalation of the ADC intermediate. All three emit deep blue light with good quantum efficiencies (
Φ
PL
= 0.13-0.48) and color profiles very close to the ideal primary blue standards for color displays.
A new structural class of mixed-carbene cyclometalated iridium complexes with intense, high-purity blue luminescence are described.
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