TY - JOUR
T1 - Polymeric end-to-end bibridged cadmium(II)thiocyanates containing monodentate and bidentate N-donor organic blockers
T2 - Supramolecular synthons based on π-π and/or C-H⋯π interactions
AU - Bose, Doyel
AU - Banerjee, Jaya
AU - Rahaman, Sk Hafijur
AU - Mostafa, Golam
AU - Fun, Hoong Kun
AU - Bailey Walsh, Rosa D.
AU - Zaworotko, Michael J.
AU - Ghosh, Barindra Kumar
PY - 2004/7/29
Y1 - 2004/7/29
N2 - 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).
AB - 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).
KW - Cadmium(II)thiocyanate
KW - Imidazole
KW - Polymer
KW - Schiff base
KW - Supramolecular synthon
UR - http://www.scopus.com/inward/record.url?scp=3543011332&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2004.04.035
DO - 10.1016/j.poly.2004.04.035
M3 - Article
AN - SCOPUS:3543011332
SN - 0277-5387
VL - 23
SP - 2045
EP - 2053
JO - Polyhedron
JF - Polyhedron
IS - 12
ER -