Synthesis and Reactivity Studies of Irida-carbolong Complexes

doi:10.6023/A20080392

Abstract

The term “carbolong complexes” represents a series of novel π-conjugating aromatic frameworks, which are formed by the chelation of a carbon chain (carbolong ligand) containing not less than 7 carbon atoms with a transition metal fragment. Carbolong complexes show unique photophysical properties, thus exhibiting promising potential applications. Inspired by the efficient strategies for the construction of Os-, Ru-, and Rh-carbolong complexes by the reactions of multiynes with simple metal sources, we describe here the reasonable design of two multiyne compounds 1 and 2, which could react with the iridium precursor [Ir(CH₃CN)(CO)(PPh₃)₂]BF₄ ( 3) to produce the irida-carbolong complexes 4 and 5 with a large π conjugation system via a “one-pot” method, respectively. This is the first time to expand the carbolong complex to iridium. In addition, the ligand substitution reactions of 4 and 5have been investigated. Treatment of corresponding ligands with 4 and 5 resulted in the generation of several new irida-carbolong complexes 6~ 9. All the prepared irida-carbolong complexes were fully characterized by NMR and HRMS. The molecular structures of the irida-carbolong complexes 4~ 8 were further confirmed by single crystal X-ray diffractions. A possible mechanism was proposed for the formation of the irida-carbolong complexes on the basis of the X-ray characterization of the key intermediate Int 2. Due to the unique large π conjugation system, all the synthesized irida-carbolong complexes exhibit remarkable absorption properties in the ultraviolet visible region, and some of them even show considerable absorption characteristics in the near infrared region (NIR). The consequently photothermal property investigation indicates that complex 5 has a good NIR photothermal effect: by measuring the temperature of its solution under the NIR laser irradiation (808 nm, 1.0 W•cm ^-2), the temperature of ethanol/water solution containing 5 (0.1 mg•mL ^-1) can be increased by nearly 40 ℃ in 10 min, providing numerous possibilities for the follow-up application research based on carbolong complexes.

Key words: carbolong complex, “one-pot” method, iridium, multiyne, photothermal property

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Jinhua Li, Qingde Zhuo, Kaiyue Zhuo, Dafa Chen, Haiping Xia. Synthesis and Reactivity Studies of Irida-carbolong Complexes[J]. Acta Chimica Sinica, 2021, 79(1): 71-80.

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Fig. & Tab. 14

Figure 1. The sketch map of 7C~12C carbolong complexes

Scheme 1. Synthesis of multiyne compounds 1 (a) and 2 (b)

Scheme 2. Synthesis of irida-carbolong complexes 4 and 5

Figure 2. Molecular structure for the cation of irida-carbolong complex 4. Ellipsoids at the 50% probability level. Counteranion and hydrogen atoms in PPh3 are omitted for clarity.

Scheme 3. Resonance structures of the irida-carbolong cations.

Figure 3. Molecular structure for the cation of irida-carbolong complex 5. Ellipsoids at the 50% probability level. Counteranion and hydrogen atoms in PPh3 are omitted for clarity.

Scheme 4. Synthesis of irida-carbolong complexes 6 and 7

Figure 4. Molecular structure for the cation of irida-carbolong complex 6. Ellipsoids at the 50% probability level. Counteranion and hydrogen atoms in PPh3 are omitted for clarity.

Figure 5. Molecular structure for the cation of intermediate Int 2. Ellipsoids at the 50% probability level. Counteranion and hydrogen atoms in PPh3 are omitted for clarity.

Scheme 5. The proposed mechanism for the formations of irida-carbolong complexes 5 and 7

Scheme 6. Synthesis of irida-carbolong complex 8

Scheme 7. The synthesis of irida-carbolong complex 9

Figure 6. UV-Vis-NIR absorption spectra of irida-carbolong complexes 4~8, measured in CH2Cl2 (1.0×10–4 mol/L) at room temperature

Figure 7. Temperature curves of solutions of irida-carbolong complexes 4 (a) and 5 (b), measured in EtOH/H2O (V(EtOH)/V(H2O)=95/5) irradiated with an 808 nm laser at a power density of 1.0 W•cm–2at the different concentrations

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