RESUMO
The strong tendency to stack in the solid state and rich luminescence for the Pt(II) complexes makes them potential candidates as new mechanochromic materials and sensing applications. Six mononuclear complexes [Pt(ppy)(O4NCS2)] (1), [Pt(bpy)(O4NCS2)]ClO4 (2), [Pt(ppy)(O5NCS2)] (3), [Pt(phen)(O4NCS2)]ClO4·CH3OH (5a), [Pt(phen)(O4NCS2)]ClO4 (5b), and [Pt(phen)(O5NCS2)]ClO4 (6a), one dinuclear complex [Pt2(phen)2(NaO5NCS2)2(ClO4)3]ClO4 (6b), and one one-dimensional (1-D) coordination polymer {[Pt2(bpy)2(NaO5NCS2)2(ClO4)2](ClO4)2}n (4) were synthesized by reacting [Pt(ppy)Cl]2, Pt(bpy)Cl2, and Pt(phen)Cl2 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and phen = 1,10-phenanthroline) with (1-aza-15-crown-5)dithiocarbamate (O4NCS2) or (1-aza-18-crown-6)dithiocarbamate (O5NCS2), respectively, which have been isolated and structurally characterized by X-ray diffraction. Neutral complexes 1 and 3 contain no intermolecular Pt(II)···Pt(II) contact, whereas cationic complexes 2, 5a, 5b, and 6a with ClO4- as counteranions show alternative intermolecular Pt(II)···Pt(II) contacts of 3.535/4.091, 3.480/5.001, 3.527/4.571, and 3.446/4.987 Å in the solid state, respectively. Interestingly, complex 4 forms a 1-D coordination polymer through coordination between the encapsulated Na+ ions inside the azacrown ether rings of O5NCS2 and ClO4- anions with respective intra- and intermolecular Pt(II)···Pt(II) contacts of 3.402 and 3.847 Å in crystal lattices, whereas a dinuclear complex 6b was surprisingly formed and also connected by the encapsulated Na+ ions and ClO4- anions with alternative intra- and intermolecular Pt(II)···Pt(II) contacts of 3.650 and 3.677/4.4.372 Å, respectively. Upon excitation, complexes 1 and 3 showed similar vibronic luminescence at 507, 534, and 502, 532 nm, respectively, and the other complexes 2 and 4-6 showed broad luminescence with maxima at 537-567 nm. The B3LYP/LanL2DZ calculation was carried out and used to clarify their excited-state properties. In addition, the powder samples for complexes 1-4 almost showed no energy shift for the luminescence and significantly those of complexes 5-6 exhibited the mechanochromic luminescence upon grinding. It is noted that complexes 5a and 6a only showed minor red shifts (i.e., from 544 to 556 nm for complex 5a and from 551 to 565 nm for complex 6a), whereas complex 6b exhibited a remarkable red shift from 558 to 603 nm upon grinding. Besides, their luminescence reversibility was also examined toward various solvents.
RESUMO
In this study, various halogen-substituted Grignard reagents were assessed as deprotonating agents for the oxazoline-amido-phenolate ligand, leading to the formation of magnesium complexes. The newly synthesized complexes with halogen substituents displayed three distinct coordinative modes, all extensively characterized through crystallographic methods. The introduction of halogen substituents induced changes in the Lewis acid properties of the complexes, thereby impacting their structural attributes and catalytic behavior during the initiation and propagation of ring polymerization of cyclic esters.
RESUMO
Our previous work applied a novel supported iron oxyhydroxide (FeOOH) catalyst to effectively treat benzoic acid by hydrogen peroxide. The FeOOH catalyst was prepared via the oxidation of Fe2+ by H2O2 in the acidic condition using a fluidized-bed crystallization reactor. The major components coated on the surface were identified as amorphous FeOOH and gamma-FeOOH. In terms of the crystallization conditions of FeOOH, some parameters including the operational pH, superficial velocity, specific iron loading, and influent H2O2 concentration were investigated to quantify their effects on the crystallization efficiency. All these parameters were found to significantly influence the crystallization efficiency. Two types of FeOOH catalysts were synthesized: FeOOH I was prepared at pH 3.5, and FeOOH II was formed by aging FeOOH I at pH 13. The percentages of surface amorphous FeOOH reduced from 70% to 30% after aging. The FeOOH II catalyst presented a higher reactivity toward H2O2 but lower stoichiometric efficiency in oxidizing benzoic acid than FeOOH I, similar to the result of the commercial goethite. Therefore, it is concluded that the crystalline property significantly affects the performance of catalytic oxidation.