Structure, Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers

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• 作者：Dmitry E. Royzman (1)
  Andrew M. Noviello (1)
  Kylie M. Henline (1)
  Robert D. Pike (1)
  James P. Killarney (2)
  Howard H. Patterson (2)
  Carlos Crawford (3)
  Zerihun Assefa (3)
  
• 关键词：Copper ; Metal–organic dimer ; Metal–organic polymer ; Luminescence ; Nucleophile ; X ; ray crystal structure ; Metal complex film
• 刊名：Journal of Inorganic and Organometallic Polymers and Materials
• 出版年：2014
• 出版时间：January 2014
• 年：2014
• 卷：24
• 期：1
• 页码：66-77
• 全文大小：772 KB
• 作者单位：Dmitry E. Royzman (1)
  Andrew M. Noviello (1)
  Kylie M. Henline (1)
  Robert D. Pike (1)
  James P. Killarney (2)
  Howard H. Patterson (2)
  Carlos Crawford (3)
  Zerihun Assefa (3)
  
  1. Department of Chemistry, College of William and Mary, Williamsburg, VA, 23187-8795, USA
  2. Department of Chemistry, University of Maine, Orono, ME, 04469-5706, USA
  3. Department of Chemistry, North Carolina A & T State University, Greensboro, NC, 27411, USA
  
• ISSN：1574-1451

文摘

The dimeric complex of Cu(I) [Cu2(PPh3)4(MeCN)2(Bpy)](BF4)2 (1a, Bpy?=?4,4-dipyridyl) self-assembles in CH2Cl2 or acetone and shows intense photoluminescence (excitation λmax?=?356?nm, emission λmax?=?486?nm, ??=?0.47). The MeCN ligands are readily removed from 1a, producing [Cu2(PPh3)4(Bpy)](BF4)2 (1b) and altering the photophysical behavior (excitation λmax?=?336?nm, emission λmax?=?568?nm, ??=?0.07). The desolvated compound 1b reversibly absorbs many vapor phase nucleophiles, as revealed by thermogravimetry. Intense luminescence emission is restored for 1b/Nu, Nu?=?MeCN (1a), acetone, tetrahydrothiophene (THT), and Et2S. Films of 1b are produced when CH2Cl2 solutions of 1a are cast onto glass. The films also react with Nu vapor, again producing intense emission. The pyrazine-bridged dimer [Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2a) is produced in CH2Cl2, while [Cu2(PPh3)4(MeCN)(acetone)(Pyz)](BF4)2??[Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2b) is formed in acetone. The crystal structure of the polymer {[Cu(PPh3)2(Bpy)](BF4)?acetone} n (3) is reported, as is the mixed polymer/dimer structure {[Cu(PPh3)2(Pyz)](BF4)} n ??em class="a-plus-plus">n[Cu2(PPh3)4(BF4)2(Pyz)] (4b) in which the dimer units show Cu–FBF3 coordination. The Pyz dimer and the Pyz and Bpy polymers show much weaker luminescence behavior than that of Bpy dimers 1a and the related 1b/Nu adducts. Nucleophile adduct structures [Cu2(PPh3)4(THT)2(Bpy)](BF4)2??ethyl ether (5) and [Cu2(PPh3)4(Py)2(Bpy)](BF4)2?CH2Cl2 (6) confirmed the coordination of one Nu per Cu to 1b.