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

详细信息    查看全文

• 作者：Jos&#xe9 ; Vicente ; Juan Gil-Rubio ; Natalia Barquero ; Peter G. Jones ; Delia Bautista
• 刊名：Organometallics
• 出版年：2008
• 出版时间：February 25, 2008
• 年：2008
• 卷：27
• 期：4
• 页码：646 - 659
• 全文大小：407K
• 年卷期：v.27,no.4(February 25, 2008)
• ISSN：1520-6041

文摘

[AuCl(SMe₂)] reacts with HCsrc="http://pubs.acs.org/images/entities/tbd1.gif">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(Csrc="http://pubs.acs.org/images/entities/tbd1.gif">CR)]_n (R = bpyl (3), phtpyl (4)). The new alkyne HCsrc="http://pubs.acs.org/images/entities/tbd1.gif">Cphccbpyl (5, phccbpyl = 4-C₆H₄Csrc="http://pubs.acs.org/images/entities/tbd1.gif">Cbpyl) has been prepared by Sonogashira coupling of 4-Me₃SiCsrc="http://pubs.acs.org/images/entities/tbd1.gif">CC₆H₄I and 1 followed by desilylation of the resulting alkyne 4-Me₃SiCsrc="http://pubs.acs.org/images/entities/tbd1.gif">Cphccbpyl. The alkynyl Au(I) complexes [Au(Csrc="http://pubs.acs.org/images/entities/tbd1.gif">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(Csrc="http://pubs.acs.org/images/entities/tbd1.gif">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 12–14 are in equilibrium with the salts [Au₃(Csrc="http://pubs.acs.org/images/entities/tbd1.gif">Cbpyl)₂(μ-Ph₂P(CH₂)_xPPh₂)₂][Au(Csrc="http://pubs.acs.org/images/entities/tbd1.gif">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(Csrc="http://pubs.acs.org/images/entities/tbd1.gif">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.