Polymeric end-to-end bibridged cadmium(II)thiocyanates containing monodentate and bidentate N-donor organic blockers: Supramolecular synthons based on π-π and/or C-H⋯π interactions

Doyel Bose, Jaya Banerjee, Sk Hafijur Rahaman, Golam Mostafa, Hoong Kun Fun, Rosa D. Bailey Walsh, Michael J. Zaworotko, Barindra Kumar Ghosh

Research output: Contribution to journalArticlepeer-review

Abstract

Treatment of Cd(NO3)2·4H2O with two equivalents of NH4NCS in combination with two equivalents of imH [imH=imidazole] or one equivalent of pfan [pfan=((pyridin-2-yl)formylidene) aniline] results neutral 1D polymers of the type [Cd(imH)2(NCS)(SCN)] n (1) or [Cd(pfan)(NCS)(SCN)]n (2). X-ray structure determinations show that in both polynuclear 1 and 2, octahedral CdII ions occupy centre of symmetry with a CdN4S2 chromophore. The metal ions are linked through N and S atoms of NCS- alternately in doubly bridged end-to-end fashion; two mutually trans N atoms of monodentate imH units complete hexacoordination of each metal centre in 1. Similar NCS-bibridging chain is present in 2 with one bidentate (N,N) Schiff base chelator (pfan) in cis orientation. The 1D chains in 1 are further engaged in intermolecular hydrogen bonding (N-H⋯S) between N of imH and coordinated S of NCS- along with aromatic π-π stacking of imH moieties that constrain the 1D chains to lie in bc-plane, which are further linked via C-H⋯π interactions. In 2, 1D chains participate in two kinds of π-π interactions. Supramers 1 and 2 display intraligand 1(π-π*) fluorescence and intraligand 3(π-π*) phosphorescence in glassy solutions (MeOH at 77 K).

Original languageEnglish
Pages (from-to)2045-2053
Number of pages9
JournalPolyhedron
Volume23
Issue number12
DOIs
Publication statusPublished - 29 Jul 2004
Externally publishedYes

Keywords

  • Cadmium(II)thiocyanate
  • Imidazole
  • Polymer
  • Schiff base
  • Supramolecular synthon

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