Two proton-conductive Cu(I) complexes based on Keggin-type clusters, [Cu(debqdc)2]2[HPW12O40]·4H2O (1), and [Cu(debqdc)2]2[HPW12O40]·debqdc·4H2O (2), where debqdc is diethyl 4,4′-dicarboxy-2,2′-biquinoline, were simply synthesized at room temperature. The products were structurally characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both complexes crystallized in the triclinic space group P−1 and presented two three-dimensional supramolecular networks with one-dimensional hydrophilic channels via hydrogen-bonding interactions and π–π stacking interactions between the aromatic rings. In the [Cu(debqdc)2]+ ion, debqdc acts as a bidentate nitrogen donor ligand in the chelating fashion. The bulky debqdc ligand constrains the Cu(I) metal center within such a rigid environment in a tetrahedral geometry. The two complexes exhibit good proton conductivities (10−5 ~ 10−4 S cm−1) at 100 °C in the relative humidity range 35 ~ 98%. The luminescence behaviors of these complexes in the solid state at room temperature have also been investigated. Upon excitation at 285 nm, both 1 and 2 display three main emission peaks centered at 470, 520, and 568 nm, respectively.
Binxiong Guang,Wei Zhang,Yiwei Zhang,Yahui Xiao,Yong Liu
A novel, efficient and economical process of cyclohexanol (CHOL) production based on cyclohexene esterification–hydrogenation has become a research hotspot in recent years. Wherein, hydrogenation of cyclohexyl acetate (CHA) derived from the esterification of cyclohexene with acetic acid is a crucial step. Combining the advantages of metal complexes and heterogeneous catalysts, the robust Cu(I) coordinated amino-functionalized poly(ionic liquid)s (PILs-Cu(I)) were, in this research, synthesized for use in the mild and highly selective hydrogenation of CHA to CHOL. The results of FT-IR, UV-vis, BET, XPS and SEM-EDS confirmed that the Cu(I) was dominant in the PILs-Cu(I), and was homogeneously and stably coordinated on the amino-functionalized poly(ionic liquid)s. Benefiting from that, the PILs-Cu(I) was endowed with an unprecedented performance in the mild and highly selective hydrogenation of CHA to CHOL. Specifically, 95.6% CHA conversion with 96.6% selectivity of CHOL, and 97.0% selectivity of ethanol was obtained under extremely mild conditions of 80 °C and 2 MPa H2. Furthermore, no significant activity loss was observed over the PILs-Cu(I) after recycling for at least five times, delivering excellent stability and reusability.
Yan Zhao,Xianying Duan,Guangguang Zhang,Meilin Wei
Two proton-conductive and luminescent organic-inorganic hybrid materials, {[Cu(II)(bhmbpy)(H2O)(Cl)0.5(CH3CN)]2[PW(VI)10W(V)2O39]}·4H2O(1) and {H2[Cu(I)(bhmbpy)2(Cl)Cu(I)(bhmbpy)2][PW12O40]}·7H2O (2) (where bhmbpy is bis(hydroxymethyl)-2,2′-bipyridine), were synthesized at room temperature. The two products were characterized by infrared spectroscopy, X-ray single-crystal diffraction, X-ray powder diffraction, elemental and thermogravimetric analyses. The proton conductivities and luminescence of 1 and 2 were studied by using alternating-current impedance spectroscopy and luminescence spectroscopy, respectively. X-ray diffraction analysis revealed that 1 includes a decorated polyanion chain {[Cu(II)(bhmbpy)(H2O)(Cl)0.5(CH3CN)]2[PW(VI)10W(V)2O39]}n and forms a three-dimensional network structure depending on short Cl…Cl contacts and hydrogen-bonding interactions. X-ray diffraction analysis revealed that 2 includes a butterfly-like bi-nuclear copper cluster unit with a Cl-bridge, [Cu(I)(bhmbpy)2(Cl)Cu(I)(bhmbpy)2]+, and forms a three-dimensional network structure depending on hydrogen-bonding interactions. [PW12O40]3– anions fill in the network based on hydrogen-bonding and electrostatic interactions. In them, the bhmbpy acts as a bidentate nitrogen donor ligand in the chelating fashion to coordinate with the Cu(II) center in 1 and the Cu(I) center in 2. The bhmbpy in 2 successfully constrains the Cu(I) within a rigid environment in a tetragonal-pyramidal geometry. The two compounds exhibit good proton conductivity (10−4 S·cm−1) at 100 °C in the relative humidity range 35–98%. Their luminescence behaviors in the solid state at room temperature have also been investigated. Upon excitation at 384 nm, 1 exhibits three emission peaks centered at 439, 507 and 566 nm. When excited at 364 nm, 2 displays three emission peaks centered at 443, 501 and 553 nm.
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