A 2,4-diarylquinoline derivative, 2-(4-chlorophenyl)-4-(3,4-dimethoxyphenyl)-6-methoxy-3-methylquinoline, was synthesized in a conventional two-step procedure from p-anisidine, p-chlorobenzaldehyde and methyl isoeugenol as available starting reagents through a sequence of BF3·OEt2-catalyzed Povarov cycloaddition reaction/oxidative dehydrogenation aromatization processes under microwave irradiation conditions in the presence of a green oxidative I2-DMSO system. The structure of the compound was fully characterized by FT-IR, 1H and 13C-NMR, ESI-MS, and elemental analysis. Its physicochemical parameters (Lipinski’s descriptors) were also calculated using the Molinspiration Cheminformatics software. The diarylquinoline molecule obtained is an interesting model with increased lipophilicity and thus permeability, an important descriptor for quinoline-based drug design. Such types of derivatives are known for their anticancer, antitubercular, antifungal, and antiviral activities.

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2-(4-Chlorophenyl)-4-(3,4-dimethoxy-phenyl)-6-methoxy-3-methylquinoline

Accessing blue-room-temperature phosphorescence from pyridine-fused extended coumarins

Room-temperature phosphorescence (RTP) from organic compounds has attracted increasing attention in the field of data security, sensing, and bioimaging. However, realization of RTP with an aggregate induced phosphorescence (AIP) feature via harvesting supersensitive excited charge transfer triplet (3CT) energy under visible light excitation (VLE) in single-component organic systems at ambient conditions remains unfulfilled. Organic donor-acceptor (D-A) based orthogonal structures can therefore be used to harvest the energy of the 3CT state at ambient conditions under VLE. Here we report three phenoxazine-quinoline conjugates (PQ, PQCl, PQBr), in which D and A parts are held in orthogonal orientation around the C-N single bond; PQCl and PQBr are substituted with halogens (Cl, Br) while PQ has no halogen atom. Spectroscopic studies and quantum chemistry calculations combining reference compounds (Phx, QPP) reveal that all the compounds in film at ambient conditions show fluorescence and green-RTP due to (i) radiative decay of both singlet charge transfer (1CT) and triplet CT (3CT) states under VLE, (ii) energetic nondegeneracy of 1CT and 3CT states (1CT- 3CT, 0.17-0.21 eV), and (iii) spatial separation of highest and lowest unoccupied molecular orbitals. Further, we found in a tetrahydrofuran-water mixture (fw = 90%, v/v) that both PQCl (10-5 M) and PQBr (10-5 M) show concentration-dependent AIP with phosphorescence quantum yields (ϕP) of ∼25% and ∼28%, respectively, whereas aggregate induced quenching (ACQ) was observed in PQ. The phosphorescence lifetimes (τP) of the PQCl and PQBr aggregates were shown to be ∼22-62 μs and ∼22-59 μs, respectively. The ϕP of the powder samples is found to be 0.03% (PQ), 15.6% (PQCl), and 13.0% (PQBr), which are significantly lower than that of the aggregates (10-5 M, fw = 90%, v/v). Film (Zeonex, 0.1 wt %) studies revealed that ϕP of PQ (7.1%) is relatively high, while PQCl and PQBr exhibit relatively low ϕP values (PQCl, 9.7%; PQBr, 8.8%), as compared with that of powder samples. In addition, we found in single-crystal X-ray analysis that multiple noncovalent interactions along with halogen···halogen (Cl···Cl) interactions between the neighboring molecules play an important role to stabilize the 3CT caused by increased rigidity of the molecular backbone. This design principle reveals a method to understand nondegeneracy of 1CT and 3CT states, and RTP with a concentration-dependent AIP effect using halogen substituted twisted donor-acceptor conjugates. 

https://pubs.acs.org/doi/pdf/10.1021/acsomega.2c01909

Thomas Berger

Papers

Phenoxazine–Quinoline Conjugates: Impact of Halogenation on Charge Transfer Triplet Energy Harvesting via Aggregate Induced Phosphorescence