Linking Tribridged Dicopper Complexes with Neutral Dipyridyl Compounds to Coordination Oligomers and Polymers

Ler Chun Shiu, Jen Han Chuang, Tian Shung Wu, Kom Bei Shiu

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The stable tribridged dicopper(I) carboxylate complexes [Cu2(μ-dppm)2(μ-O2CR)]BF4 (RCO2 = formate (OFc), m1; acetate (OAc), m2; benzoate (OBAc), m3; o-toluate (O2TAc), m4; p-toluate (O4TAc), m5; 4-phenylbutyrate (O4PBAc), m6; 2-nitrobenzoate (O2NBAc), m7), abbreviated as MM, and neutral dipyridyl compounds (NN; NN = 4,4′-bipyridine (bpy), 1,2-bis(4-pyridyl)ethane (bpa), trans-1,2-bis(4-pyridyl)ethylene (bpe), 4,4′-trimethylenedipyridine (tmp)) can form dynamic equilibria in CH2Cl2. From the equilibrium mixtures containing MM and NN with MM/NN = 1:1, nine 2:1 oligomers ([(m1)2(μ-bpy)](BF4)2 (o1a(BF4)2), [(m3)2(μ-bpe)](BF4)2 (o3c(BF4)2), [(m3)2(μ-tmp)](BF4)2 (o3d(BF4)2), [(m4)2(μ-bpe)](BF4)2 (o4c(BF4)2), [(m5)2(μ-bpy)](BF4)2 (o5a(BF4)2), [(m5)2(μ-tmp)](BF4)2 (o5d(BF4)2), [(m6)2(μ-bpa)](BF4)2 (o6b(BF4)2), [(m7)2(μ-bpy)](BF4)2 (o7a(BF4)2), [(m7)2(μ-bpa)](BF4)2 (o7b(BF4)2)), one 2:3 oligomer ([{(m2)(bpy)}2(μ-bpy)](BF4)2 (o2a(BF4)2)), and five 1:1 polymers ([(m2)(μ-bpe)] n (BF4) n (p2c(BF4) n), [(m2)(μ-tmp)] n (BF4) n (p2d(BF4) n), [(m3)(μ-bpy)] n (BF4) n (p3a(BF4) n), [(m3)(μ-tmp)] n (BF4) n (p3d(BF4) n), [(m7)(μ-tmp)] n (BF4) n (p7d(BF4) n)) were obtained as single crystals, and their structures were determined by X-ray crystallography. Both experimental and theoretical results support the presence of two oligomeric species, [{Cu2(μ-dppm)2(μ-O2CR)}2(μ-NN)]2+ and [{Cu2(μ-dppm)2(μ-O2CR)(NN)}2(μ-NN)]2+), in dynamic equilibrium. The oligomers (such as o3d(BF4)2) can serve as seeds to induce the formation of soluble coordination polymers as crystals (such as p3d(BF4)n).

Original languageEnglish
Pages (from-to)61-72
Number of pages12
JournalJournal of the Chinese Chemical Society
Volume64
Issue number1
DOIs
Publication statusPublished - 2017 Jan 1

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Linking Tribridged Dicopper Complexes with Neutral Dipyridyl Compounds to Coordination Oligomers and Polymers'. Together they form a unique fingerprint.

  • Cite this