Triple-Columned and Multiple-Layered 3D Polymers: Design, Synthesis, Aggregation-Induced Emission (AIE), and Computational Study

Abstract

Conjugated polymers and oligomers have great potentials in various fields, especially in materials and biological sciences because of their intriguing electronic and optoelectronic properties. In recent years, the through-space conjugation system has emerged as a new assembled pattern of multidimensional polymers. Here, a novel series of structurally condensed multicolumn/multilayer 3D polymers and oligomers have been designed and synthesized through one-pot Suzuki polycondensation (SPC). The intramolecularly stacked arrangement of polymers can be supported by either X-ray structural analysis or computational analysis. In all cases, polymers were obtained with modest to good yields, as determined by GPC and 1H-NMR. MALDI-TOF analysis has proven the speculation of the step-growth process of this polymerization. The computational study of ab initio and DFT calculations based on trimer and pentamer models gives details of the structures and the electronic transition. Experimental results of optical and AIE research confirmed by calculation indicates that the present work would facilitate the research and applications in materials.

Asymmetric Catalytic Assembly of Triple‐Columned and Multilayered Chiral Folding Polymers Showing Aggregation‐Induced Emission (AIE)

“…This compacted packing model contributed to more effective through‐space π–π interactions, thus offsets partial AIE activities. This result was consistent with our previous study on racemic polymers [15a] …”

“…Based on the above work, we investigated polymerizations leading to structurally compacted triple‐columned/multilayered polymers and oligomers along with the corresponding aggregation‐induced emission (AIE) properties and computational studies. Multistep Suzuki–Miyaura cross‐coupling [19] has been proven to be efficient in one‐pot strategy for this polymerization (Figure 1B) [15a] . Interestingly, regular loops on the surfaces of vials were observed when the solution of certain trimer was slowly evaporated in the open air, which provided a macro clue of the ordered intermolecular stacking [20] .…”

Multilayer 3D Chiral Folding Polymers and Their Asymmetric Catalytic Assembly

“…In our previous design of multiple-layered 3D polymers, the bridges between column anchors were either symmetrically or nonsymmetrically substituted aromatic rings on their 1,4-position [ 25 ]. In the present design, the derivatives of 1,8-dibromonaphthalene were employed as building blocks alternatively together with benzo[c] [ 1 , 2 , 5 ], thiadiazole and benzo[c] [ 1 , 2 , 5 ], and selenodizole scaffolds [ 26 ].…”

Aggregation-Induced Polarization (AIP): Optical Rotation Amplification and Adjustment of Chiral Aggregates of Folding Oligomers and Polymers

“…The origin of AIE was made possible by restricting intramolecular motions (rotation and vibration) which limit or avoid aggregation-caused quenching (ACQ) of conventional luminophores. During our ongoing projects on multiple-layered 3D folding chirality, we found that chiral aggregates of folding monomers, oligomers, and polymers displayed strong AIE by gradually increasing water fractions (f w ) in THF-H 2 O cosolvents (Wu et al, 2019;Liu et al, 2020;Wu et al, 2020;Wu et al, 2021a;Wu et al, 2021b;Tang et al, 2022b;Jin et al, 2022;Wang et al, 2022). Interestingly, we also found these polymers showed AIE curves bounding when f w was increased to 70%, which contrast with the observation of their monomer derivatives (Wu et al, 2021b;Wang et al, 2022).…”