Two new hexacoordinated coordination polymers of cadmium(II) containing bridging units only: Syntheses, structures and molecular properties

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• 作者：DIPU SUTRADHAR ; HABIBAR CHOWDHURY ; SUSHOVAN KONER…
• 关键词：Cadmium(II) ; coordination polymers ; benzidine ; thiocyanate ; X ; ray structures ; luminescence.
• 刊名：Journal of Chemical Sciences
• 出版年：2016
• 出版时间：September 2016
• 年：2016
• 卷：128
• 期：9
• 页码：1377-1384
• 全文大小：1,164 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Chemistry
  
• 出版者：Springer India
• ISSN：0973-7103
• 卷排序：128

文摘

The syntheses, characterizations and structures of a neutral 2D coordination polymer [Cd(bnzd)(NCS)₂]_n (1) and a polycationic 3D coordination polymer isolated as perchlorate salt [Cd(bnzd)₃]_n(ClO₄)_2n (2) (bnzd = benzidine) are described. X-ray structural analyses reveal that each hexacoordinated cadmium(II) center in 1 adopts a distorted octahedral geometry with a CdN₄S₂ chromophore bound by two N atoms of two different bnzd units and two N and two S atoms of symmetric doubly bridged end-to-end NCS − units extended in a 2D sheet. Six N atoms of six different bridged bnzd units are bonded to each cadmium(II) in 2 in a non-ended fashion affording a 3D network structure. In the crystalline state, each 2D sheet structure in 1 is further stabilized by π⋯π interaction which in turn affords a 3D network structure through multiple intermolecular N-H ⋯S hydrogen bonds. On the other hand, the 3D network structure in 2 is stabilized by weak intermolecular N-H ⋯O hydrogen bonds and C-H ⋯π interactions. Bnzd, 1 and 2 display intraligand 1(π- π*) fluorescence in DMF solution at room temperature.