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Synthesis of Luminescent Alkynyl Gold Metalaligands Containing 2,2′-Bipyridine-5-yl and 2,2′:6′,2′′-Terpyridine-4-yl Donor Groups

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posted on 25.02.2008, 00:00 by José Vicente, Juan Gil-Rubio, Natalia Barquero, Peter G. Jones, Delia Bautista
[AuCl(SMe2)] reacts with HCCR (R = bpyl = 2,2′-bipyridine-5-yl (1), phtpyl = phenyl-4-(2,2′:6′,2′′-terpyridine-4-yl) (2)) and NEt3 (1:1:3) to afford the polymers [Au(CCR)]n (R = bpyl (3), phtpyl (4)). The new alkyne HCCphccbpyl (5, phccbpyl = 4-C6H4CCbpyl) has been prepared by Sonogashira coupling of 4-Me3SiCCC6H4I and 1 followed by desilylation of the resulting alkyne 4-Me3SiCCphccbpyl. The alkynyl Au(I) complexes [Au(CCR)L] (R = bpyl, L = PPh3 (6), PTol3 (7, Tol = 4-MeC6H4), PEt3 (8); R = phtpyl, L = XyNC (9), PPh3 (10); R = phccbpyl, L = PPh3 (11)) have been prepared by reacting: (1) 3 or 4 with L or (2) the corresponding alkyne 1, 2, or 5 with [Au(acac)(PPh3)] (acac = acetylacetonato). The reaction of 3 or 4 with diphosphines gives [{Au(CCR)}2(μ-Ph2P(CH2)xPPh2)] (R = bpyl, x = 1 (12), 2 (13), 4 (14), 10 (15); R = phtpyl, x = 10 (16)). ESI mass spectrometric studies show that complexes 1214 are in equilibrium with the salts [Au3(CCbpyl)2(μ-Ph2P(CH2)xPPh2)2][Au(CCbpyl)2], although only when x = 1 (17) was a significant concentration of the salt detected by NMR spectroscopy and isolated. The anionic complexes PPN[Au(CCR)2] (R = bpyl (18), phtpyl (19), or phccbpyl (20)) have been prepared by reaction of the corresponding alkynes with PPN[Au(acac)2]. Complexes 6, 10, 13, 14, 17, and 18 have been characterized by single-crystal X-ray diffraction studies. The alkynyl complexes are luminescent at room temperature, displaying dual emissions.

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