Syntheses, structures and luminescence behaviours of Group 12 metal(II) thiocyanate complexes with a tetradentate Schiff base: Variation in molecular and crystalline architectures with the change of congeneric metal ions

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• 作者：Sumitra Das^a ; Kishalay Bhar^a ; Soumi Chattopadhyay^a ; Partha Mitra^b ; Vincent J. Smith^c ; Leonard J. Barbour^c ; ^{ljb@sun.ac.za} ; Barindra K. Ghosh^a ; ^{barin_1@yahoo.co.uk}
• 关键词：Group 12 metal(II) ; Thiocyanate ; Schiff base ; S· ; · ; · ; S/S· ; · ; · ; 蟺 interaction ; Luminescence
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：11 May, 2012
• 卷：38
• 期：1
• 页码：26-35
• 文件大小：1919 K

摘要

One pentacoordinated mononuclear complex [Zn(L)(NCS)]PF₆ (1), one hexacoordinated 2D coordination polymer {[Cd₂(L)(NCS)₄]路0.24(CH₃OH)}_n (2) and one pentacoordinated 1D polymeric chain [Hg₂(L)(SCN)₄]_n (3) [L = N,N鈥?(bis(pyridine-2-yl)benzylidene)-1,4-butanediamine] have been synthesized and X-ray crystallographically characterized. Structural analyses revealed interesting variations in the coordination behaviour of the Schiff base (L) from tetradentate chelation to binucleating bis(bidentate) congregation on going from 1 to 2/3. The pseudohalide exhibits terminal N-coordination in 1, both 渭_1,3 and 渭_1,1 bridges in 2 and terminal S-coordination along with 渭_1,1 linkages in 3. In 1/3, each pentacoordinated zinc(II)/mercury(II) centre adopts a distorted trigonal bipyramidal/square pyramidal geometry with a ZnN₅/HgN₂S₃ chromophore, whereas both Cd1 and Cd2 centres in 2 adopt a distorted octahedral geometry with CdN₃S₃ and CdN₆ chromophores, respectively. Weak intermolecular S路路路S and S路路路蟺 interactions with multiple C-H路路路N hydrogen bonds promote the dimensionalities in 1-3. The complexes display intraligand ¹(蟺-蟺^{鈭?/sup>) fluorescence in the solid state and in DMF solutions at room temperature.}