Defang Xu

Low-dimensional nanostructures fabricated from bis(dioxaborine)carbazole derivatives as fluorescent chemosensors for detecting organic amine vapors

New triphenylamine functionalized bis(dioxaborine)carbazole derivatives (BDOBCn, n = 4, 8, 16) have been synthesized, and low-dimensional nanostructures with different morphologies have been fabricated from BDOBCn with carbon chains of different lengths. For example, 1D single-crystalline nanowires are generated from BDOBC4via a reprecipitation approach, 1D nanofibers based on BDOBC16 are prepared through an organogelation process, and amorphous nanoparticles are obtained from BDOBC8. It is interesting that the films formed from the obtained nanostructures can give strong fluorescence emission under irradiation and can act as fluorescent chemosensors for probing aniline vapors, with different response rates and different sensitivity controlled by their morphologies. The mesh-like film obtained from the BDOBC16-based gel exhibits faster fluorescent response in milliseconds and higher sensitivity than the nanoparticle- and nanowire-based films, because the supramolecular objects primarily formed in the gelling process percolate and fill the entire volume at a low-over all-volume fraction, and the entangled piling of the fibers leads to increased porosity. Thus, it not only provides a large surface for enhanced adsorption and accumulation of gaseous molecules but also enables expedient cross-film diffusion of gaseous species. Notably, the organogel fibers of BDOBC16 allow high selectivity for probing aniline vapor, and the detection limit reaches 8.6 ppm.

New dendritic gelator bearing carbazole in each branching unit: selected response to fluoride ion in gel phase

A new dendritic gelator with carbazole as the building block (HBCD) was synthesized. It was found that H-bonding between the amide groups and π-π interaction between the aromatic rings played predominant roles in the gel formation. Meanwhile, significant aggregation-induced emission enhancement was observed in the gel state due to the formation of J-aggregates and the restricted molecular motion. Notably, the gel state of HBCD can be destroyed upon addition of F(-), accompanied by fluorescence enhancement on account of the formation of N-HF(-), which could further lead to the increased coplanarity of HBCD. The sensory capability of HBCD exhibited a high selectivity towards F(-) instead of the Cl(-), Br(-), I(-) and AcO(-) anions, which could be explained by the fact that the steric hindrance of the dendrimer would go against the interactions between the larger anions and HBCD.

Self-assembly of a chiral lipid gelator controlled by solvent and speed of gelation.

Glutamine derivative 1 with two-photon absorbing units has been synthesized and was found to show gelation ability in some solvents. Its self-assembly in the gel phase could be controlled by the solvent and speed of gelation. For example, in DMSO the organogelator self-assembled into H-aggregates with weak exciton coupling between the aromatic moieties. On the other hand, in DMSO/diphenyl ether (1:9, v/v) the molecules formed 1D aggregates, but with strong exciton coupling due to the small distance between the chromophores. Moreover, the formation of these two kinds of aggregates could be adjusted by the ratio of DMSO to diphenyl ether. In DMSO/toluene, DMSO/butanol, DMSO/butyl acetate, and DMSO/acetic acid systems similar results were observed. Therefore, conversion of the packing model occurs irrespective of the nature of the solvent. Notably, a unique sign inversion in the CD spectra could be realized by controlling the speed of gelation in the DMSO/diphenyl ether (1:9, v/v) system. It was found that a low speed of gelation induces the gelator to adopt a packing model with strong pi-pi interactions between the aromatic units. Moreover, the gels, when excited at 800 nm, emit strong green fluorescence and the quantum chemical calculations suggest that intramolecular charge transfer leads to two-photon absorption of the gelator molecule.

Luminescent Organic 1D Nanomaterials Based on Bis(β‐diketone)carbazole Derivatives

A series of new triphenylamine-functionalized bis(β-diketone)s bridged by a carbazole (CnBDKC, n=1, 4, 8, 16) with twisted intramolecular charge-transfer emission in polar solvents has been synthesized. The length of the carbon chains has a significant effect on the self-assembling properties of the compounds. Well-defined 1D nanowires were easily generated from C1BDKC with a methyl group by a reprecipitation approach directed by π-stacking interaction, and the molecules packed into J-aggregates in the nanowires. In addition, 1D nanofibers based on C16BDKC bearing a long hexadecyl chain were prepared through the organogelation process, and H-aggregates were formed driven by the synergistic effect of π-stacking interaction and van der Waals force in the gel phase. C4BDKC and C8BDKC containing butyl and octyl side chains, respectively, cannot arrange into dispersed nanostructures, probably because π-π interaction between conjugated moieties might be disturbed by the interaction between the side chains, which is, however, not strong enough to dominate the self-assembling process. Notably, the nanowires based on C1BDKC and the gel nanofibers from C16BDKC can emit strong green light under irradiation, which suggests that these 1D nanomaterials may have potential applications in emitting materials as well as photonic devices.

Carbazole-based organogel as a scaffold to construct energy transfer arrays with controllable fluorescence emission.

A diaryldiketopyrrolopyrrole derivative functionalized with phenothiazine moieties (DPPP) was synthesized and introduced into the ordered 4-(3,6-di-tert-butyl-9H-carbazol-9-yl)benzamide (TBCB) organogel system. It was found that TBCB-based gel became a scaffold to make DPPP molecules line up along the gel fibers, resulting in new self-assembled arrays, whose XRD patterns were quite different from those of the neat TBCB gel and DPPP crystal. In the composite gel, the occurrence of a partial energy transfer from the excited light-harvesting antenna of TBCB to the DPPP acceptor was confirmed on the basis of time-dependent and time-resolved fluorescence investigations. Remarkably, the composite gel could emit intense red light or purplish white light by tuning the excitation wavelength. Such ordered soft materials with color-tunable emission may possess potential applications in sensor and photonic devices.

Hybrid Self-Assembly of a π Gelator and Fullerene Derivative with Photoinduced Electron Transfer for Photocurrent Generation

A pi-conjugated organogelator (1) was synthesized, and its gelation ability was checked. It was found that it is an excellent gelator for some organic solvents, such as dichloromethane, benzene, o-dichlorobenzene, and DMSO/water. It can self-assemble into 1-D nanofibers induced by hydrogen bonding and pi-pi interactions. Moreover, 1 could form a hybrid gel with C(60)COOH by hydrogen bonds in which 1 and C(60)COOH can act as an electron donor and acceptor, respectively. It was found that the active film from the hybrid 1-D self-assemblies of 1 and C(60)COOH showed remarkably higher photocurrent generation compared with that containing 1 and C(60) because of the construction of interdigitated and ordered assemblies of donors and acceptors.