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Synlett 2010(1): 61-66  
DOI: 10.1055/s-0029-1218554
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Johanna Hummela, Andreas Winterb,c, Anja Baumgaertelc,d, Nikolaus Rischa, Ulrich S. Schubert*b,c,d
a Chemistry Department, Faculty of Science, Paderborn University, Warburger Str. 100, 33098 Paderborn, Germany
b Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
c Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands
d Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstr. 10, 07743 Jena, Germany
Fax: +49(3641)948202; e-Mail: ulrich.schubert@uni-jena.de;
Further Information

Publication History

Received 12 July 2009
Publication Date:
09 December 2009 (online)

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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

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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 (mc, 4 H), 8.55 (mc, 2 H), 8.42 (d, ³ J = 8.4 Hz, 2 H), 8.38 (mc, 4 H), 8.11 (d, ³ J = 8.4 Hz, 2 H), 8.06 (mc, 2 H), 7.93 (mc, 6 H), 7.82-7.52 (m, 10 H), 7.37-7.21 (m, 8 H), 7.14 (mc, 2 H), 6.95 (mc, 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.