Carbolong Complexes are compounds formed by a planar conjugated carbon chain (carbon number ≥ 7) chelating a transition metal through at least 3 carbon-metal bonds. In 2013, Professor Xia Haiping's research group synthesized and named this type of compound for the first time [1]. This work was selected as one of the "Top Ten Scientific and Technological Progress in Chinese Universities" in 2013. Subsequently, the research group expanded and constructed a series of new molecular skeletons of 7-13 carbon chain chelating metals [2,3], which were called "Carbon Dragon Flush" by colleagues (Figure 1), and gradually established a Chinese The unique “Carbon Dragon Chemistry”. Carbolong’s entry has been reported by C&E News and selected into the latest English edition of the international classic textbook “March’s Advanced Organic Chemistry”.

Figure 1 Carbon Dragon Flush

Carbolong complexes have multiple reaction sites and rich reactivity, and can be structurally modified and derivatized through common chemical reactions. For example, 7C-carbolong complex can undergo metal carbene addition reaction with electrophiles, nucleophiles and alkynes to obtain a series of carbolong complexes [1,4-8]; 8C-carbolong complex can Ring-opening and ring-expansion reactions occur with unsaturated substrates such as alkynes and allenes to obtain 7C, 10C, and 12C- respectively. Carboron complexes and other metal heterocyclic compounds [9-14]; 12C-carboron complex can undergo aromatic electrophilic substitution reaction with halogen electrophiles to obtain halogenated 12C-carboron complex [15]. Suzuki–Miyaura coupling reaction with arylboronic acid can also be continued [16]. Carbolong complexes can be directly prepared by chelating chain polyynes (Carbolong Ligands) with metals, which not only greatly simplifies the synthesis route of Carbolong compounds, but also expands the metal varieties of Carbolong chemistry from osmium to Rhodium, ruthenium, iridium and other transition metals [17-22].

Aromatic systems with metals embedded in the skeleton (including carbotron species) have attracted much attention due to the participation of d electrons in transition metals in delocalization. Due to reasons such as difficulty in synthesis and insufficient water and oxygen stability, there has been no research on their properties and applications before. Professor Xia Haiping's research group broke through the two major bottlenecks of the synthesis and stabilization of carbolong complexes, and took the lead in conducting and leading the research on the performance of metal heteroaromatic systems in the world, making this field a big step towards application expansion. Structure determines performance, and performance determines application. The performance of carbon dragon comes from its two major structural features:

Figure 2 Structure-activity relationship of Carbolanium species—two major structural features deriving four categories of uses

1.Platinum group metals are located within the aromatic ring: the metal center has a catalytic function. For example, the bimetallic osmium-copper carboron complex can catalyze the difunctionalization reaction of non-activated alkenes, and more than 80 organic selenium compounds with potential biological significance have been synthesized, demonstrating the application potential of carboron complexes in the field of catalysis [23 ]. In addition, carbolon peroxy complex can catalyze the activation of oxygen, and then use photoactivation to treat hypoxic tumors [24,25].

2.Unique dπ-pπ conjugation: It has a broad and strong absorption spectrum, which can absorb light waves in a wide frequency range and convert them into light, electricity, heat and ultrasonic waves. It has good application prospects in fields such as solar energy utilization and tumor phototherapy. For example: 7C-Carbonon complex has near-infrared emission > 300 nm It has the characteristics of Stokes shift, long luminescence lifetime, and AIE effect [1]; 12C-Carbonon complex can be used for tumor photoacoustic labeling and photothermal therapy, and has passed experiments on mice [11,26]; some Carbolon complexes For example, phenanthroline biscarbron complex and 12C-carbron complex are used in organic and perovskite solar cell materials [8, 20, 27-32], and their device PCEs are greater than 18% and 23% respectively.

Based on the above two structural characteristics, carbolong complexes are used in homogeneous catalysis [23,24], solar cells [8,20,27-32] (organic, perovskite), and molecular electronics research [33,34 ], responsive polymer materials [35,36], biomedicine [6,11,25] (photoacoustic imaging, photothermal therapy and photodynamic therapy) and photothermal seawater desalination [37] and other fields have been applied (Figure 3).

Figure 3 Research results on properties and applications of carbonate complexes

After years of painstaking research, Professor Xia Haiping's research group has developed a series of original carbon dragon complexes with unique structures and excellent performance. Bailingwei exclusively provides some of the carbon dragon compound products developed by Professor Xia Haiping's research group to help carbon dragon chemistry develop! Product advantages are as follows:

Simple synthesis: Carboron complexes can be prepared through a one-pot method of polyyne carbon chain and metal chelation [17-22];
Diverse structures: Carbolong complexes are rich in reactivity and can be used to obtain a series of functional molecules through pre-modification and post-derivatization functionalization [2];
Unique performance: Because the d electrons of the metal participate in delocalization, a unique dπ-pπ conjugation is formed, which shows different properties from traditional organic aromatic systems [3][3].

Product list

Product name：
8C Carbolong complex, 95%
CAS：1667743-98-7
Item number：9307661
application：Functional Carbon Dragon Blocks

8C-carboron complex can react with various substrates such as alkynes, alkenes, allenes, and organic heterocycles for ring opening and ring expansion to obtain various metal heterocycles such as 7C, 10C, and 12C-carboron complexes. Compound [9-14] is a functional carbon dragon building block with rich reactions.

Product name：
12C Carbolong complex, 95%
CAS：2917610-83-2
Item number：9307662
application：Photothermal and photoacoustic materials

12C-Carbonon complex has a broad and strong absorption spectrum in the ultraviolet-visible-near-infrared region, excellent light-heat/light-acoustic conversion efficiency, and good stability, and can be used for photoacoustic labeling and photothermal treatment of tumors. , thereby realizing the integration of tumor diagnosis and treatment, and has currently passed experiments on mice [11,26].

Product name：
Carbolong peroxo complex, 95%
CAS：2244156-01-0
Item number：9307663
application：Catalytic oxygen activation, photodynamic materials

Carbohydron peroxy complex can catalyze the activation of oxygen and realize the catalytic oxidation of alcohol [24]. At the same time, the carbonium peroxygen complex also has excellent photodynamic properties and can be used to treat hypoxic tumors by photoactivation [25].

Product name：
Os-Cu Carbolong complex, 95%
CAS：2225872-98-8
Item number：9307664
application：metal catalyst

Osmium-copper carbonium complexes benefit from the synergistic effect of bimetals and can be used as catalysts to achieve difunctionalization reactions of non-activated alkenes. More than 80 organic selenium compounds with potential biological significance have been synthesized, demonstrating the synergistic effect of carbonon complexes. Application potential in the field of catalysis [23].

Product name：
Phenanthroline-Carbolong, 95%
CAS：N/A
Item number：9307665
application：Electron transport layer materials

The phenanthroline biscarbide complex is an electron transport layer material with excellent performance. When applied to organic solar cells, it can achieve a photoelectric conversion efficiency of 18.2%. At the same time, the phenanthroline biscarbacron complex will not interact with the active layer acceptor material. reaction, which can significantly increase the stability of the device [30].

References

1. Nature Chem. 2013, 5, 698.
2. Acc. Chem. Res. 2018, 51, 1691.
3. Acc. Chem. Res. 2023, 56, 924.
4. Nat. Commun. 2014, 5, 3265.
5. Angew. Chem., Int. Ed. 2014, 53, 6232.
6. Angew. Chem., Int. Ed. 2015, 54, 6181.
7. J. Am. Chem. Soc. 2017, 139, 1822.
8. Nat. Commun. 2020, 11, 4651.
9. Angew. Chem., Int. Ed. 2015, 54, 3102.
10. Angew. Chem., Int. Ed. 2015, 54, 7189.
11. Sci. Adv. 2016, 2, e1601031.
12. Angew. Chem., Int. Ed. 2017, 56, 9067.
13. Nat. Commun. 2019, 10, 1488.
14. Angew. Chem., Int. Ed. 2022, 61, e202211734.
15. Proc. Natl. Acad. Sci. U. S. A. 2021, 118, e2102310118.
16. Chem. Sci. 2023, 14, 1227.
17. Nat. Commun. 2017, 8, 1912.
18. Sci. Adv. 2018, 4, eaat0336.
19. iScience 2019, 19, 1214.
20. J. Am. Chem. Soc. 2021, 143, 7759.
21. J. Am. Chem. Soc. 2021, 143, 15587.
22. J. Am. Chem. Soc. 2023, 145, 7580.
23. J. Am. Chem. Soc. 2022, 144, 2301.
24. iScience 2020, 23, 101379.
25. Nat. Commun. 2022, 13, 2245.
26. J. Mater. Chem. B 2018, 6, 2528.
27. Adv. Mater. 2021, 33, e2101279.
28. Adv. Funct. Mater. 2023, 33, 2300359.
29. Adv. Sci. 2022, 9, 2203640.
30. Nat. Commun. 2023, DOI: 10.1038/s41467-023-39223-9.
31. Angew. Chem., Int. Ed. 2023, 135, e202305489.
32. Nano-Micro Lett. 2023, DOI:10.1007/s40820-023-01130-5.
33. J. Am. Chem. Soc. 2017, 139, 14344.
34. J. Am. Chem. Soc. 2023, 145, 10404.
35. ACS Macro Lett. 2018, 7, 1034.
36. ACS Macro Lett. 2020, 9, 344.
37. SusMat 2022, 2, 679.