Cyclopenta[hi]aceanthrylenes (CPAs) have been functionalized at two of the peripheral positions with electronically inert trimethylsilylethynyl (1), as well as with electron-donating 4-ethynyl-N,N-dimethylaniline (2), ethynyl Zn phthalocyanine (3), and ethynyl Zn porphyrin (4) units. Consistent with X-ray crystal structures of 2 and 4, analyses of absorption and fluorescence of 2-4 point to strong electronic communication between the CPA and the peripheral units, affording quadrupolar electron donor-acceptor-donor charge-transfer conjugates. By virtue of their quadrupolar/dipolar charge-transfer characters in the excited state, 2-4 exhibit fluoro-solvatochromism. Transient absorption spectroscopy confirmed delocalized quadrupolar ground states and formation of weakly solvent stabilized quadrupolar singlet excited states. The latter transform into strongly stabilized dipolar excited states before deactivating to the ground state in 2 and give rise to a fully charge separated state in 3 and 4.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.201906206 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Chalcogen Substitution-Modulated Molecule-Electrode Coupling in Single-Molecule Junctions.
Langmuir
January 2025
Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province, School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, 928 Second Street, Zhejiang, Hangzhou 310018, China.
Molecule-electrode interfaces play a pivotal role in defining the electron transport properties of molecular electronic devices. While extensive research has concentrated on optimizing molecule-electrode coupling (MEC) involving electrode materials and molecular anchoring groups, the role of the molecular backbone structure in modulating MEC is equally vital. Additionally, it is known that the incorporation of heteroatoms into the molecular backbone notably influences factors such as energy levels and conductive characteristics.
View Article and Find Full Text PDFPhotoredox-Mediated Immunotherapy Utilizing Rhenium(I) Photocatalysts with Electron Donor-Acceptor-Donor Configuration.
J Med Chem
January 2025
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, China.
The hypoxic environment of solid tumors significantly diminishes the therapeutic efficacy of oxygen-dependent photodynamic therapy. Developing efficient photosensitizers that operate photoredox catalysis presents a promising strategy to overcome this challenge. Herein, we report the rational design of two rhenium(I) tricarbonyl complexes ( and ) with electron donor-acceptor-donor configuration.
View Article and Find Full Text PDFMolecularly manipulating pyrazinoquinoxaline derivatives to construct NIR-II AIEgens for multimodal phototheranostics of breast cancer bone metastases.
Biomaterials
January 2025
Center for AIE Research, Guangdong Provincial Key Laboratory of New Energy Materials Service Safety, College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518060, China; School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen (CUHK-Shenzhen), Guangdong, 518172, China. Electronic address:
Multimodal phototheranostics on the basis of single molecular species shows inexhaustible and vigorous vitality, particularly those emit fluorescence in the second near-infrared window (NIR-II), the construction of such exceptional molecules nonetheless retains formidably challenging. In view of the undiversified molecular skeletons and insufficient phototheranostic outputs of previously reported NIR-II fluorophores, herein, electron acceptor engineering based on heteroatom-inserted rigid-planar pyrazinoquinoxaline was manipulated to fabricate aggregation-induced emission (AIE)-featured NIR-II counterparts with donor-acceptor-donor (D-A-D) architecture. Systematical investigations substantiated that one of those synthesized AIE molecules, namely 4TPQ, incorporating a fused thiophene acceptor, synchronously exhibited high molar absorptivity (ε), NIR-II emission, typical AIE tendency, significant reactive oxygen species (ROS) generation, and high photothermal conversion efficiency.
View Article and Find Full Text PDFDesign, Synthesis, and Imaging of a Stable Xanthene-Based Dye with NIR-II Emission up to 1450 nm.
Anal Chem
January 2025
Center for Advanced Materials Research & Faculty of Arts and Sciences, Beijing Normal University, Zhuhai 519087, P. R. China.
The development of long-wavelength near-infrared II (NIR-II, 900-1700 nm) dyes is highly desirable but challenging. To achieve both red-shifted absorption/emission and superior imaging capabilities, a donor-acceptor-donor (D-A-D) xanthene core was strategically modified by extending π-conjugated double bonds and enhancing electron-donating properties. Two dyes named and were synthesized and exhibited notably red-shifted absorption/emission peaks at 942/1250 and 1098/1450 nm, respectively.
View Article and Find Full Text PDFPyrrolopyrrole Cyanine Aggregates with Amplified Superoxide Radical Generation, GSH Depletion, and Photothermal Action for Hypoxic Cancer Phototherapy.
ACS Appl Mater Interfaces
January 2025
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, P. R. China.
The elevated glutathione (GSH) level and hypoxia in tumor cells are two key obstacles to realizing the high performance of phototherapy. Herein, the electron-donating rotors are introduced to wings of electron-withdrawing pyrrolopyrrole cyanine (PPCy) to form donor-acceptor-donor structure -aggregates for amplified superoxide radical generation, GSH depletion, and photothermal action for hypoxic cancer phototherapy to tackle this challenge. Three PPCy photosensitizers (PPCy-H, PPCy-Br, and PPCy-TPE) produce hydroxyl radicals (•OH) and superoxide radicals (O) in hypoxia tumors exclusively as well as excellent photothermal performances under light irradiation.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!