4.6 Article

Macrocyclic NiII-Xanthate [NiII2-μ2-bis-{(κ2S,S-S2COCH2CH2)2N(Ts)}] Complex and a Cyclic Thiocarbonate Monomer: Synthesis, Crystallography, Photophysical, TD-DFT and Investigation of Thermochromism

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JOURNAL OF MOLECULAR STRUCTURE
卷 1287, 期 -, 页码 -

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ELSEVIER
DOI: 10.1016/j.molstruc.2023.135657

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Organic; inorganic macrocycles; XRD; Thermochromism; Electrochemical; TD-DFT

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The potassium salt of N,N-Bis(2-dithiocarbonatoethyl)-4-methylbenzenesulfon amide (K2xan) was successfully synthesized and characterized. A plausible mechanism for the formation of compound 2 was established based on experimental evidence. The coordination geometry around the NiII center in compound 1 was found to change from a distorted square planar to an octahedral complex depending on the solvent.
Potassium salt of N,N-Bis(2-dithiocarbonatoethyl)-4-methylbenzenesulfon amide (K2xan) was synthesized and characterized prior to use in the progress of a 24-membered binuclear metallomacrocyclic compound [NiII2-mu 2-bis-{(kappa 2S,S-S2COCH2CH2)2N(Ts)}] (1) and a synthetically challenging 16-member organic functional macrocycle 6,14-ditosyl-1,3,9,11-tetraoxa-6,14-diaza-cyclohexadecane-2,10-dithione (2). Compounds have been character-ized by using microanalysis, standard spectroscopic and crystallographic techniques. A plausible mechanism for the formation of compound 2 has been established based on experimental evidence. Compounds 1 and 2 fluo-resces at 377 and 293 nm upon excitation at 314 and 232 nm, respectively. The single crystal X-ray diffraction (SCXRD) study revealed a distorted square planar coordination geometry around NiII-centre in 1 which is consistent in the solution of non-coordinating solvents such as CH2Cl2. In a coordinating solvent such as DMSO, however, charge transfer bands 421, 481 nm vanished and characteristic d-d transition band at 698 nm appeared which suggest a change in the coordination geometry around NiII centre from square planar (in CH2Cl2) to octahedral complex (in DMSO). This solvatochromic behaviour of NiII-xanthate complex 1 is supplemented by reversible thermochromic behaviour over a wide temperature ca 30-90 degrees C. Notably, thermal degradation of NiII- xanthate complex 1 gave a stable residual mass that corresponds to NiS. The X-band EPR, UV-visible and TD-DFT studies and electrochemical investigations have been performed to rationalize the results and establish the structure-property correlation.

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