The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu<sup>+</sup>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Co<sup>3+</sup> chloride and/or iodi...The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu<sup>+</sup>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Co<sup>3+</sup> chloride and/or iodide afford new metal complexes. The isolated complexes were synthesized by two different techniques (chemical and tribochemical methods). Two complexes were synthesized by the direct chemical reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) with MCl<sub>2</sub>·XH<sub>2</sub>O (M = Co<sup>2+</sup> and Cu<sup>2+</sup>;X = 6 in case of Co<sup>2+</sup> and X = 2 in case of Cu<sup>2+</sup>) in absolute EtOH. The general formulae of the two complexes derived by the chemical method are [Cu(L)<sub>2</sub>(EtOH)<sub>2</sub>]Cl<sub>2</sub> and [Co(L)<sub>2</sub>Cl<sub>2</sub>]Cl. These complexes were used to synthesize another two complexes using tribochemical reaction by grinding the previous chloride complexes with excess KI in agate mortar in the solid state. The isolated complexes have the general formulae, [Cu(L)I·H<sub>2</sub>O]·1/2H<sub>2</sub>O and [Co(L)I<sub>3</sub>(Et- OH)]·3EtOH. The results indicate the substitution of the chloride by iodide ions during grinding and extraction of the complexes by solvents. The IR spectra of the complexes suggest that L acts in a bidentate manner towards the metal ions. Moreover, the results of electronic spectra and magnetic measurements for the chloride complexes suggest distorted-octahedral structure for Cu<sup>2+</sup> and low-spin octahedral structures around the Co<sup>II</sup> and Cu<sup>2+</sup> ions, respectively. On the other hand the data suggest that the iodide complexes have square-planer and low-spin for the Cu<sup>+</sup> and Co<sup>3+</sup> ions, respectively. The results of mass spectra confirm the formulae proposed for the isolated complexes. The mechanisms of reduction of Cu<sup>II</sup> and oxidation of Co<sup>II</sup> for the metal complexes were elucidated.展开更多
Herein,we demonstrated that poly（ethylene oxide）（PEO）,urea and thiourea can crystallize into novel ternary complex with the molar ratio of vip polymer and host small molecule as 3：2,and proved that the ternary ...Herein,we demonstrated that poly（ethylene oxide）（PEO）,urea and thiourea can crystallize into novel ternary complex with the molar ratio of vip polymer and host small molecule as 3：2,and proved that the ternary complex behaves isomorphism phenomenon by varying the ratio between urea and thiourea for the first time.This observation gives a boost to prepare co-crystals of different small molecules that cannot be obtained by direct mixing without the aid of polymer chains.展开更多
文摘The reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) derived from with Cu<sup>+</sup>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Co<sup>3+</sup> chloride and/or iodide afford new metal complexes. The isolated complexes were synthesized by two different techniques (chemical and tribochemical methods). Two complexes were synthesized by the direct chemical reactions of N-(O-hydoxyphenyl)-N'-phenylthiourea (L) with MCl<sub>2</sub>·XH<sub>2</sub>O (M = Co<sup>2+</sup> and Cu<sup>2+</sup>;X = 6 in case of Co<sup>2+</sup> and X = 2 in case of Cu<sup>2+</sup>) in absolute EtOH. The general formulae of the two complexes derived by the chemical method are [Cu(L)<sub>2</sub>(EtOH)<sub>2</sub>]Cl<sub>2</sub> and [Co(L)<sub>2</sub>Cl<sub>2</sub>]Cl. These complexes were used to synthesize another two complexes using tribochemical reaction by grinding the previous chloride complexes with excess KI in agate mortar in the solid state. The isolated complexes have the general formulae, [Cu(L)I·H<sub>2</sub>O]·1/2H<sub>2</sub>O and [Co(L)I<sub>3</sub>(Et- OH)]·3EtOH. The results indicate the substitution of the chloride by iodide ions during grinding and extraction of the complexes by solvents. The IR spectra of the complexes suggest that L acts in a bidentate manner towards the metal ions. Moreover, the results of electronic spectra and magnetic measurements for the chloride complexes suggest distorted-octahedral structure for Cu<sup>2+</sup> and low-spin octahedral structures around the Co<sup>II</sup> and Cu<sup>2+</sup> ions, respectively. On the other hand the data suggest that the iodide complexes have square-planer and low-spin for the Cu<sup>+</sup> and Co<sup>3+</sup> ions, respectively. The results of mass spectra confirm the formulae proposed for the isolated complexes. The mechanisms of reduction of Cu<sup>II</sup> and oxidation of Co<sup>II</sup> for the metal complexes were elucidated.
基金Financial support from the National Natural Science Foundation of China(Nos.21304108 and 21674128)
文摘Herein,we demonstrated that poly（ethylene oxide）（PEO）,urea and thiourea can crystallize into novel ternary complex with the molar ratio of vip polymer and host small molecule as 3：2,and proved that the ternary complex behaves isomorphism phenomenon by varying the ratio between urea and thiourea for the first time.This observation gives a boost to prepare co-crystals of different small molecules that cannot be obtained by direct mixing without the aid of polymer chains.
