Flexible and shape-selective guest binding at CuII axial sites in 1-dimensional CuII-1,2-bis(4-pyridyl)ethane coordination polymers

Shin Ichiro Noro, Satoshi Horike, Daisuke Tanaka, Susumu Kitagawa, Tomoyuki Akutagawa, Takayoshi Nakamura

Research output: Contribution to journalArticlepeer-review

32 Citations (Scopus)

Abstract

A series of guest-binding CuII coordination polymers, {[Cu(bpetha)2(acetone)2]·2PF6} n (bpetha = 1,2-bis(4-pyridyl)-ethane) (1), {[Cu(bpetha) 2(DMF)2]·2PF6}n (2), {[Cu(bpetha)2(MeCN)2]·2PF6·2MeCN} n (3), {[Cu(bpetha)2(H2O)2] ·2PF6·3THF·2H2O}n (4), {[Cu(bpetha)2(H2O)2]·2PF 6·3dioxane}n (5), and {[Cu(bpetha) 2(H2O)2]·2PF6·2- PrOH·2H2O}n (6), have been synthesized and crystallographically characterized. Their framework stabilities and guest-exchange properties have also been investigated. All compounds form a similar framework motif, a "double chain", in which the bpetha ligands bridge CuII centers to form 1-D [Cu(bpetha)2]n double chains. A variety of Lewis base guest molecules, such as H2O, acetone, DMF, MeCN, THF, dioxane, and 2-PrOH, are incorporated into the assembly of the 1-D double chains. These chains flexibly change their forms of assembly in a guest-dependent manner. Interestingly, acetone, DMF, and MeCN guests with a carbonyl or cyanide group coordinate directly to the axial sites of the CuII centers; in contrast, THF, dioxane, and 2-PrOH guests with an ether or alcohol group are incorporated into the frameworks not via coordination bonds but via weak interactions (hydrogen bonds and van der Waals forces). This selectivity is probably due to steric effects at coordinated oxygen or nitrogen atoms of the guests. Crystal-to-crystal transformations triggered by guests are observed, during which guests coordinated to the Cu II axial sites are readily removed and replaced by other guests.

Original languageEnglish
Pages (from-to)9290-9300
Number of pages11
JournalInorganic chemistry
Volume45
Issue number23
DOIs
Publication statusPublished - 2006 Nov 13
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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