Synthesis, molecular and crystalline architectures, and properties of a mononuclear complex [Co II (benzidine) 2 (NCS)

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• 作者：SUBHASISH KUNDU ; SUBHASIS ROY ; KISHALAY BHAR…
• 关键词：Cobalt(II) ; thiocyanate ; benzidine ; X ; ray structure ; magnetism
• 刊名：Journal of Chemical Sciences
• 出版年：2013
• 出版时间：July 2013
• 年：2013
• 卷：125
• 期：4
• 页码：723-730
• 全文大小：641KB
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• 作者单位：SUBHASISH KUNDU (1)
  SUBHASIS ROY (1)
  KISHALAY BHAR (1)
  RAJARSHI GHOSH (1)
  CHIA-HER LIN (2)
  JOAN RIBAS (3)
  BARINDRA KUMAR GHOSH (1)
  
  1. Department of Chemistry, The University of Burdwan, Burdwan, 713 104, India
  2. Depatrment of Chemistry, Chung Yuan Christian University, Chung Li, Taiwan, 32023, ROC
  3. Departament de Química Inorgánica, Universitat de Barcelona, Diagonal, 647; 08028, Barcelona, Spain
  
• ISSN：0973-7103

文摘

One mononuclear cobalt(II) compound of the type [Co(bnzd)2(NCS)2(OH2)2] (1) (bnzd = benzidine) has been isolated through a single-pot reaction of the molecular building components in MeOH–H2O solvent mixture at room temperature and characterized by physico-chemical and spectroscopic methods. The crystal structure of complex 1 has an octahedral geometry with trans, trans, trans orientations in the order (Na,Na), (Nt,Nt), (Ow,Ow) [Na = N(amine), Nt = N(thiocyanate) and Ow = O(water)]. In crystalline state, individual units of 1 are associated by weak cooperative O–H...N, O–H...S and N–H...S hydrogen bonds resulting in a 3D network structure. The compound is redox active and shows luminescence in MeOH solution. Thermal decomposition pattern of 1 reveals the presence of two coordinated water molecules. Variable-temperature magnetic susceptibility measurement shows significant orbital contribution and numerical matrix diagonalization method gives the best fit parameters: α = A*k = 1.43; λ-??130?cm??-; Δ-??-64?cm??-; TIP?= 0.000975; R = 1.19 × 10??-. Graphical Abstract Mononuclear compound [Co(benzidine)2(NCS)2(OH2)2] (1) was isolated and characterized. Cobalt(II) center adopts an octahedral geometry and individual units of 1 are associated by weak O–H…N/S and N–H…S hydrogen bonds resulting in a 3D network structure. Complex 1 is electroactive and shows luminescence property. Variable-temperature magnetic property shows significant orbital contribution.