New Ditopic Ligands Containing 2,2′:6′,2′′-Terpyridine and a Rigid U-/S-Shaped Terpyridine

Abstract

The modular approaches towards 2,2′:6′,2′′-terpyridines and U-/S-shaped terpyridines are combined to yield a new family of ditopic ligands. Functionalized Kröhnke-type terpyridines were used as key building blocks for the construction of hetero-bis(terpyr­idine)s. The described compounds might serve as new templates for the self-assembly towards new metallosupramolecular functional materials.

Key words

cross-coupling - iminium salts - Mannich reaction - supramolecular chemistry - terpyridines

References and Notes

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18

The signal at δ = 2.76 ppm is a superposition of the expected methylene proton and DMSO that could not be fully removed after the reaction and purification procedure.

25

Synthesis of [(tpy)Ru(12)Ru(tpy)](PF ₆ ) ₄
A suspension of(tpy)RuCl₃ (20.3 mg, 0.046 mmol)^²³ and 12 (15.0 mg, 0.022 mmol) in ethylene glycol (10 mL) was heated under microwave irradiation at 150 ˚C for 2 h. The reaction mixture was poured into H₂O (10 mL) and filtered. Subsequently, an excess of NH₄PF₆ (50 mg) was added, and the formed dark red precipitate was isolated. The crude product was purified by preparative size exclusion chroma­-
tography (BioBeads SX-3, acetone as eluent) to yield the dinuclear complex (28 mg, 67%). ^¹H NMR (400 MHz, CD₃CN): δ = 8.97 (s, 2 H), 8.72 (m_c, 4 H), 8.55 (m_c, 2 H), 8.42 (d, ^³ J = 8.4 Hz, 2 H), 8.38 (m_c, 4 H), 8.11 (d, ^³ J = 8.4 Hz, 2 H), 8.06 (m_c, 2 H), 7.93 (m_c, 6 H), 7.82-7.52 (m, 10 H), 7.37-7.21 (m, 8 H), 7.14 (m_c, 2 H), 6.95 (m_c, 2 H), 3.35-3.02 (m, 8 H) ppm. MALDI-TOF MS (matrix: dithranol):
m/z = 1627.40 [M - 2PF₆]⁺, 1482.27 [M - 3PF₆]⁺, 1002.99 [(tpy)Ru(12)]⁺, 768.19 [Ru(12)]⁺. Anal. Calcd for C₇₆H₅₄F₂₄N₁₂P₄Ru₂: C, 47.61; H, 2.84; N, 8.77. Found:
C, 47.92; H, 3.11; N, 8.92.