Syntheses and Properties of Heteroatom-Doped Conjugated Nanohoops

doi:10.6023/cjoc202205006

Abstract

As structural models for carbon nanotube segments, radially conjugated carbon nanohoops have received much attention from chemists, which led to a series of bottom-up synthetic strategies. However, most of these nanohoops are composed only of benzene and simple polyaromatic hydrocarbon moieties. Modulation of the optoelectronic properties is mainly dependent on the variation of ring size, which greatly limits the functional development and application of conjugated nanohoops. In recent years, syntheses and property study of heteroatom-doped carbon nanohoops have become a new research hotspot. The design, synthesis and properties of conjugated nanohoops involving heterocyclic subunits such as pyridine, thiophene, furan, carbazole, benzothiadiazole, chrysenylene, 1,2-azaborine heterocycle, diketopyrrolopyrrole, porphyrin, perylene diimide, and naphthodithiophene diimide, etc. are reviewed. Most of these nanohoops have special topological structures. The introduction of heteroatoms not only significantly improves their optoelectronic properties, but also regulates their assembly, leading to new skeletons for multifunctional supramolecular systems and organic materials.

Key words: carbon nanohoops, radial conjugation, aromatic heterocycle, heteroatom-doping

Cite this article

Huijun Zhang, Jianbin Lin. Syntheses and Properties of Heteroatom-Doped Conjugated Nanohoops[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3437-3455.

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Fig. & Tab. 21

Figure 1. History of research on macrocyclic compounds

Figure 2. Design of columnar nanocyclic structures based on aromatic heterocyclic units

Figure 3. Bent precursor-aromatization strategies

Figure 4. Organometallic macrocyclization strategies

Figure 5. Synthesis of conjugated nanohoops containing pyridine or 2,2'-bipyridine moieties

Entry	Compound	λ_max^a/nm	ε/(L•mol^－1•cm^－1)	λ_em/nm	E_HOMO^b/eV	E_LUMO^b/eV
1	13a (aza[8]CPP)	345	2.8×10⁴	541	－5.25	－2.03
2	13b (1,15-diaza[8]CPP)	349	9.2×10⁴	544	－5.27	－2.08
3	13c (1,15,31-triaza[8]-CPP)	353	1.1×10⁴	542	－5.31	－2.15
4	[13a-Me]OTf	345	2.9×10⁴	598	－5.36	－2.92
5	[13b-Me₂]OTf₂	350	4.9×10⁴	630	－5.63	－3.07
6	13d (aza[6]CPP)	342	5.5×10⁴	—	－4.98	－2.14
7	[13d-Me]OTf	343	2.3×10⁴	—	－5.39	－2.86

Table 1. Comparison of the photoelectric properties of 13a~13d before and after N-methylation

Figure 6. Synthesis of o-phenanthroline-containing nanohoops

Figure 7. Synthesis of nanohoops containing five-membered heterocycles

Entry	Compound	λ_max/nm	ε/(L•mol^－1•cm^－1)	λ_em/nm	Φ_F/%	E_HOMO^a/eV	E_LUMO^a/eV
1	25a ([4]CPT)	333 (C₆H₁₂)	—	546	—	－5.01	－1.74
2	25b ([5]CPT)	350 (C₆H₁₂)	—	510	—	－5.00	－1.82
3	25c ([6]CPT)	362 (C₆H₁₂)	—	488	—	－4.97	－1.90
4	27a ([3]CP₂T)	346 (THF)	2.4×10⁴	523	27	－5.04	－1.76
5	27b ([4]CP₂T)	354 (THF)	3.7×10⁴	472	37	－5.13	－1.71
6	28a ([3]CP₂S)	365 (THF)	2.1×10⁴	560	8	－5.01	－1.82
7	28b ([4]CP₂S)	370 (THF)	2.8×10⁴	492	13	－5.13	－1.78
8	29 ([3]CP₂E)	371 (THF)	2.7×10⁴	555	34	－4.61	－1.65

Table 2. Comparison of the optoelectronic properties of conjugated nanorings [n]CPT, [n]CP2T, [n]CP2S and [n]CP2E containing thiophene or selenophene units

Figure 8. Synthesis of carbazole- and dibenzothiophene-containing nanohoops (the spectral data were measured in CHCl3)

Figure 9. Synthesis of carbazole-containing capped and lemniscular-shaped nanohoops (the spectral data were measured in CH2Cl2)

Figure 10. Synthesis of benzothiadiazole-containing nanohoops and bilayer nanohoops (the spectral data were measured in CH2Cl2 or CHCl3)

Figure 11. Synthesis of 1,8-diazopyrene- and chrysenedithiophene-containing nanohoops

Figure 12. Synthesis of 1,2-azaborine heterocycle-containing nanohoops (the spectral data were measured in CH2Cl2)

Figure 13. Synthesis of diketopyrrolopyrrole-based donor-acceptor nanohoops C-DPP

Figure 14. Synthesis of porphyrin-based conjugated nanohoops

Entry	Compound	λ_max^a/nm	ε^a/(L•mol^－1•cm^－1)	E_HOMO^b/eV	E_LUMO^b/eV
1	87a ([3]CP)	409	2.4×10⁵	－5.0	－2.4
2	87b ([4]CP)	414	3.0×10⁵	－5.0	－2.5
3	87c ([5]CP)	423	4.4×10⁵	－5.0	－2.4
4	89a ([3]CPB)	435	2.8×10⁵	－5.0	－2.3
5	89b ([4]CPB)	430	4.3×10⁵	－5.1	－2.3
6	89c ([5]CPB)	428	7.5×10⁵	－5.1	－2.2
7	89d ([6]CPB)	427	1.2×10⁵	－5.1	－2.2

Table 3. Comparison of the optoelectronic properties of [n]CP and [n]CPB

Figure 15. Synthesis of PDI-based conjugated nanohoops

Figure 16. Design principles for columnar conjugated nanotubes

Figure 17. Synthesis of [4]C-NDTI, and (b) crystal structure and 2D packing mode of 105-A4

Figure 18. Six possible isomers of [4]C-NDTI (the orientation of the NDTI units marked as A and B with different color, respectively)

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