The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crysta...The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.展开更多
Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural phot...Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.展开更多
The reported X-ray structure and magnetochemical properties of [Mn6O2 (OCPh)10, (CH3CN)4], effectively derived from [NBu4][Mn4O2(O2CPh)9 (H2O)] with equivalent of tren in CH3CN is shown.
Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on...Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.展开更多
Four isostructural M^(Ⅲ)_(4) Ln^(Ⅲ)_(2) coordination clusters,[M_(4)Ln_(2)(μ_(3)-OH)_(2)(nbdea)_(4)(C_(6)H_(5)COO)_(8)]·MeCN (M=Fe,Ln=Er (1);M=Ga,Ln=Er (2);M=Fe,Ln=Ho (3);M=Ga,Ln=Ho (4)) have been synthesized ...Four isostructural M^(Ⅲ)_(4) Ln^(Ⅲ)_(2) coordination clusters,[M_(4)Ln_(2)(μ_(3)-OH)_(2)(nbdea)_(4)(C_(6)H_(5)COO)_(8)]·MeCN (M=Fe,Ln=Er (1);M=Ga,Ln=Er (2);M=Fe,Ln=Ho (3);M=Ga,Ln=Ho (4)) have been synthesized and characterized. Single-crystal X-ray diffraction and X-ray powder diffraction studies revealed that all four compounds crystallize isomorphously to each other,and to the previously reported M_(4)^(Ⅲ) Dy_(2)^(Ⅲ) (M=Fe or Ga) and Fe_(4)^(Ⅲ) Y_(2)^(Ⅲ) analogues. DC magnetic susceptibility measurements for compounds 1–4,taken in combination with those for the Fe^(Ⅲ)_(4) Y^(Ⅲ)_(2) analogue,indicated that the interactions between Er^(Ⅲ) ions are weakly ferromagnetic and the Fe^(Ⅲ)–Er^(Ⅲ) interactions are very weakly antiferromagnetic,while the Ho^(Ⅲ)–Ho^(Ⅲ) and Fe^(Ⅲ)–Ho^(Ⅲ) interactions are both negligible. By comparison,for the Fe^(Ⅲ)_(4) Dy^(Ⅲ)_(2) analogue,the Dy^(Ⅲ)–Dy^(Ⅲ) interactions are antiferromagnetic while the Fe^(Ⅲ)–Dy^(Ⅲ) are ferromagnetic. Both Er analogues 1 and 2 display single-molecule magnet (SMM) behavior with the effective energy barrier Ueff increasing from 12.8 K (for Fe_(4)Er_(2) 1) to 53.5 K (for Ga_(4)Er_(2) 2),indicating that the very weak 3d–4f interaction enhances the QTM effect.展开更多
基金Nanjing University of Posts and Telecommunications (No. NY209032)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education,Science Foundation for Youths of Guangxi Province (No. 0991089)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.
文摘Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.
文摘The reported X-ray structure and magnetochemical properties of [Mn6O2 (OCPh)10, (CH3CN)4], effectively derived from [NBu4][Mn4O2(O2CPh)9 (H2O)] with equivalent of tren in CH3CN is shown.
文摘Compound[(n-C4H9)4N]3 [Mo6O18(N2C6H4-pNO2)] crystallizes in the orthorhombic space grou Pnma with a= 23. 964(9).b=16.948(4),c=17.968(7) A,V=7298(7) A3,Z=4,and Dc=1.58 g/cm-3. Structure solution and refinement based on 3113 reflections with I>3.0σ(I) gave final residuals of R= 0.072 and Rω=0.099.The anion is a substitution isopolymolybdate.
文摘Four isostructural M^(Ⅲ)_(4) Ln^(Ⅲ)_(2) coordination clusters,[M_(4)Ln_(2)(μ_(3)-OH)_(2)(nbdea)_(4)(C_(6)H_(5)COO)_(8)]·MeCN (M=Fe,Ln=Er (1);M=Ga,Ln=Er (2);M=Fe,Ln=Ho (3);M=Ga,Ln=Ho (4)) have been synthesized and characterized. Single-crystal X-ray diffraction and X-ray powder diffraction studies revealed that all four compounds crystallize isomorphously to each other,and to the previously reported M_(4)^(Ⅲ) Dy_(2)^(Ⅲ) (M=Fe or Ga) and Fe_(4)^(Ⅲ) Y_(2)^(Ⅲ) analogues. DC magnetic susceptibility measurements for compounds 1–4,taken in combination with those for the Fe^(Ⅲ)_(4) Y^(Ⅲ)_(2) analogue,indicated that the interactions between Er^(Ⅲ) ions are weakly ferromagnetic and the Fe^(Ⅲ)–Er^(Ⅲ) interactions are very weakly antiferromagnetic,while the Ho^(Ⅲ)–Ho^(Ⅲ) and Fe^(Ⅲ)–Ho^(Ⅲ) interactions are both negligible. By comparison,for the Fe^(Ⅲ)_(4) Dy^(Ⅲ)_(2) analogue,the Dy^(Ⅲ)–Dy^(Ⅲ) interactions are antiferromagnetic while the Fe^(Ⅲ)–Dy^(Ⅲ) are ferromagnetic. Both Er analogues 1 and 2 display single-molecule magnet (SMM) behavior with the effective energy barrier Ueff increasing from 12.8 K (for Fe_(4)Er_(2) 1) to 53.5 K (for Ga_(4)Er_(2) 2),indicating that the very weak 3d–4f interaction enhances the QTM effect.
