Synthesis and spectral characterization of bimetallic metallomacrocyclic structures [MII2-μ2-bis-{(κ2S, S-S2CN(R)C6H4)2O}] (M = Ni/Zn/Cd): density functional theory and host–guest reactivity studies. Issue 129 (16th December 2015)

• Record Type: Journal Article
• Authors: Kadu, Rahul; Pillai, Vineeta; V., Amrit; Singh, Vinay K.
• Is Part Of: RSC advances. Volume 5:Issue 129(2015)
• Page Start: 106688
• Page End: 106699
• Publication Date: 2015-12-16
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c5ra22175g
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Compounds displayed the ability to form 1 : 1 host–guest inclusion complexes with bidentate guests and to form metal sulphides on thermal degradation. Abstract : A series of bimetallic dithiocarbamate metallomacrocyclic complexes [M II 2 -μ 2 -bis-{(κ 2 S, S -S2 CN(R)C6 H4 )2 O}]·L {R = benzyl; M = Ni II 1, Zn II 2, Cd II 3 ; R = 1-naphthylmethyl; M = Ni II 4, Zn II 5, Cd II 6 and L = Et3 N for1, 4 only} were efficiently synthesized through a self-assembly process involving 4, 4′-bis(arylmethylamino)diphenyl ethersL 1, L 2, CS2 and M(OAc)2 . The compounds were characterized by micro-, relevant spectroscopic (ESI-MS, FT-IR, 1 H, 13 C and 1 H DOSY NMR, UV-visible absorption, fluorescence) and TGA/DTA analyses. The geometry of all the complexes has been optimized by a DFT method with B3LYP/LanL2DZ basis sets. Notably, the fluorescence properties ofL 1 andL 2 were enhanced upon complexation with Ni, Zn or Cd metal ions in the binuclear complexes1–6 . Ni II complexes1 and4 gave stable residual masses of 20.1% and 29.5% in their thermogravimetric analyses which correspond to NiS (calc. 14.18% for1 and 12.26% for4 ) plus char, respectively. A Job plot experiment reveals the ability of macrocycles1–4 to form host–guest complexes in 1 : 1, 1 : 2 and 2 : 1 stoichiometry, depending on the relative sizes of the hosts and guests and their electronic nature.