Facile synthesis and platinum complexes of 4′,5,5′′-trisubstituted-2,2′:6′,2′′-terpyridines

Abstract

The synthesis of trisubstituted 4',5,5'' terpyridines is described. The strategy begins with synthesis of 2-acetyl-5-bromopyridine (3) from 2,5-dibromopyridine, substitution of the bromine in 3 using a variety of metal-catalyzed reactions and then formation of the terpyridine using the Krohnke reaction. The complexes have been prepared by reaction of [Pt(PhCN)(2)Cl(2)] with the appropriate silver salt followed by addition of the terpyridyl ligand. The crystal structure of two complexes have been determined via X-ray diffraction and the MLCT (metal-to-ligand charge-transfer) emissions determined by UV/Vis spectroscopy.

trans-(Aniline-κN)dichlorido(dimethyl sulfoxide-κS)platinum(II)

“…A slight distortion from planarity is indicated with a dihedral angle of 4.39 (11) between the Cl2-Pt1-S1 and Cl1-Pt1-N1 planes. The Pt1-N1, 2.081 (3) Å , Pt1-S1, 2.2206 (10) Å , and the two Pt-Cl bond distances Pt1-Cl1 2.2894 (11) Å , and 2.2933 (11) Å are normal and comparable to values reported for related Pt II complexes in the literature (Francisco et al, 2011;Rahman et al 2015;Huo et al 2011).…”

Using geometric simulation software ‘GASP’ to model conformational flexibility in a family of zinc metal–organic frameworks

“…All reagents were purchased from commercial sources and used as received except for 2-acetyl-5-bromopyridine, which was synthesised following a known literature procedure. 13 4-(6-Acetylpyridin-3-yl)benzoic acid A suspension of 4-carboxyphenylboronic acid (0.896 g, 5.4 mmol), 2-acetyl-5-bromopyridine (1.080 g, 5.4 mmol), K 2 CO 3 (2.0 g, 14.5 mmol) and [Pd(PPh 3 ) 4 ] (0.150 g, 0.13 mmol) in a mixture of water and methanol (1 : 2 v/v, 50 mL) was heated to reflux overnight under an atmosphere of nitrogen. The reaction mixture was then cooled to room temperature and filtered to remove the catalyst.…”

“…1 H-NMR (300 MHz, DMSO-d 6 ): d = 10.05 (s, 1 H, CHO), 6 H,PhH), 7.86 (d, J = 9.0 Hz, 2 H, PhH) ppm. 13 DMSOd 6 ): 192.76,167.04,144.66,142.88,135.64,130.66,130.21,130.07,127.73,127.35 To a 10 mL microwave vial were added 4-(6-acetylpyridin-3-yl) benzoic acid (500 mg, 2.07 mmol), 4 0 -formyl-[1,1 0 -biphenyl]-4carboxylic acid (234 mg, 1.03 mmol), potassium hydroxide (250 mg, 4.46 mmol) and a 2 : 1 mixture of water and conc. aq.…”

Unsymmetrically functionalized 5,5″-diaryl- and 5,6,5″-triaryl-2,2′:6′,2″-terpyridines: an efficient synthetic route and photophysical properties

“…12 In some cases the Krenke method was used, wherein the starting 2-acetyl-5-arylpyridines were synthesized by the combinations of cross-coupling reactions (for the introduction of aryl substituents), and the subsequent reactions of pyridyl-lithium intermediates with acetyl chloride for the introduction of acetyl group. 2,13 It is worthy to mention that among these reported methods only few of them 12,14 afforded the unsymmetrically functionalized 5,5''-diaryl-2,2':6',2''-terpyridines.…”

“…2,3 Thus, many examples were reported of using these compounds as chromophores in phosphorescent europium complexes, 4 as well as chemosensors for metal cations. 5 In addition, some terpyridine-based liquid crystal materials were described.…”