A new carboxylate-phosphonate, [Zn3（O3PCH（CH3）COO）2（H2O）] 1, has been successfully synthesized by hydrothermal technique and characterized by X-ray single-crystal structure analysis, elemental analysis and infra...A new carboxylate-phosphonate, [Zn3（O3PCH（CH3）COO）2（H2O）] 1, has been successfully synthesized by hydrothermal technique and characterized by X-ray single-crystal structure analysis, elemental analysis and infrared spectroscopy. It crystallizes in monoclinic, space group P2 1/c with a = 4.9521（5）, b = 21.953（3）, c = 13.2266（18） A, β = 100.704（2）°, V= 1412.9（3） A3, Z= 4, Mr = 516.19, Dc= 2.427 g/cm^3, F（000） = 1016,μ（MoKα） = 5.332 mm^-1 and T= 293（2） K. The final R = 0.0605 and wR = 0.1354 for 2957 observed reflections with I 〉 2σ（I）. The thermogravimetric analysis （TGA） and fluorescent measurement have been done. The structure of compound 1 is a 3D open framework with 32-atom channels.展开更多
One new Ni（Ⅱ） complex [Ni（H2L）]Cl（H2O）3 based on one in-situ synthesized Schiff base ligand H3L （H3L = bis（benzyl-2-pyridylidene）-diaminoguanidine） was prepared and structurally characterized by single-crys...One new Ni（Ⅱ） complex [Ni（H2L）]Cl（H2O）3 based on one in-situ synthesized Schiff base ligand H3L （H3L = bis（benzyl-2-pyridylidene）-diaminoguanidine） was prepared and structurally characterized by single-crystal X-ray diffraction method. The complex crystallizes in the monoclinic system, space group C2/c with a = 27.944（7）, b = 7.7405（19）, c = 25.999（7） ,A, β = 115.545（2）°, V = 5074（2） A^3, Mr = 566.69, Z = 8, Dc = 1.484 g/cm^3, F（000） = 2352,μ（MoKα） = 0.912 mm^-1, R = 0.0594 and wR = 0.1477 for 5145 observed reflections （1 〉 2σ（I））. The complex exhibits one mononuclear structure in which the Ni（Ⅱ） atom adopts a [NiN4] pseudo-planar square geometry. Interestingly, along the b axis, each two neighboring [Ni（H2L）]^＋ units by an inverse center form pairs of molecules through the intermolecular benzene-pyridine π…π interactions.展开更多
The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe)...The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.展开更多
We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2)...We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2);n=1,3[PF6]_(2);n=5,4[PF6]_(2)) by using a mononuclear complex[PY5Me_(2)Ru(μ-CN)][PF_(6)](1) as the precursor.All the three complexes have been fully characterized by including single-crystal X-ray diffraction analysis.The one-electron oxidation complexes 2^(3+),3^(3+) and 4^(3+) obtained in situ all show a MMCT absorption band in the visible range.The MMCT energy increases as the redox potential of the N-terminal fragments decreases,and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases,supported by the TDF/TDDFT calculations.展开更多
To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer(MMCT)properties in similar mixed-valence(MV)complexes,a series of binuclear organo...To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer(MMCT)properties in similar mixed-valence(MV)complexes,a series of binuclear organometallic complexes,MeCp(dppe)RuCNFeCl_(3)(1),MeCp(PPh_(3))_(2)RuCNFeCl_(3)(2),Cp^(*)(dppe)FeCNFeCl_(3)(3),Cp^(*)(dppe)RuCNFeCl_(3)(4)and Cp^(*)(PPh_(3))_(2)RuCNFeCl_(3)(5),have been synthesized and characterized.The electronic absorptions of these complexes show the presence of MMCT properties between RuⅡ or FeⅡ and FeⅢ ions,strongly supported by the theoretical calculations.With increasing electron-donating ability of ligands(PPh3>dppe,Cp^(*)>MeCp)at donor site,the MMCT absorption bands are red-shifted,which expresses in the sequence of absorption bands with 1(500 nm),4(536 nm),2(542 nm),5(580 nm)from high-energy to low-energy.Meanwhile,the MMCT absorption energy of 4(536 nm)is larger than that of 3(760 nm)due to the stronger electron-donating ability of FeⅡ than RuⅡ.Furthermore,these complexes belong to the Class Ⅱ systems according to the Robin and Day’s classification.展开更多
Three dinuclear cyanide-bridged complexes[Fe^(Ⅱ)(PY_(5)OMe_(2))CNM^(Ⅱ)(PY_(5)OMe_(2))](OTf)_(3) (M=Fe1,M=Co 2,M=Mn 3)(PY_(5)OMe_(2)=2,6-bis-((2-pyridyl)methoxymethane)pyridine OTf=CF_(3)SO_(3)^(-)) have been synthes...Three dinuclear cyanide-bridged complexes[Fe^(Ⅱ)(PY_(5)OMe_(2))CNM^(Ⅱ)(PY_(5)OMe_(2))](OTf)_(3) (M=Fe1,M=Co 2,M=Mn 3)(PY_(5)OMe_(2)=2,6-bis-((2-pyridyl)methoxymethane)pyridine OTf=CF_(3)SO_(3)^(-)) have been synthesized and characterized.Single-crystal diffraction analyses show these three dinuclear compounds are very similar in structure.The measured ν(CN) results for compounds 1~3 suggest that Mn^(2+) is electron-poorer than Fe^(2+) and Co^(2+).Meanwhile,the temperature dependence of magnetic susceptibilities of complexes 1~3 reveals that in these three complexes,all the cyanide-carbon coordinated Fe(Ⅱ) is low-spin,and Co(Ⅱ) for 2 and Mn(Ⅱ) for 3are both in a high-spin state through 2~400 K but the cyanide-nitrogen coordinated Fe(Ⅱ) for complex 1 exhibits spin crossover (SCO) behavior over 300 K and a hysteresis of 36 K in both cooling and heating modes.展开更多
基金This research was supported by the State Key Laboratory of Structural Chemistry, the National Ministry of Science and Technology of China (001CB1089), the Chinese Academy of Sciences (CAS), the National Natural Science Foundation of China (20333070 and 90206040), the Natural Science Foundation of CAS and Fujian Province (2005HZ01-1, 2004HZ01-1, 2003J042, 2004J041 and Z0513022)
文摘A new carboxylate-phosphonate, [Zn3（O3PCH（CH3）COO）2（H2O）] 1, has been successfully synthesized by hydrothermal technique and characterized by X-ray single-crystal structure analysis, elemental analysis and infrared spectroscopy. It crystallizes in monoclinic, space group P2 1/c with a = 4.9521（5）, b = 21.953（3）, c = 13.2266（18） A, β = 100.704（2）°, V= 1412.9（3） A3, Z= 4, Mr = 516.19, Dc= 2.427 g/cm^3, F（000） = 1016,μ（MoKα） = 5.332 mm^-1 and T= 293（2） K. The final R = 0.0605 and wR = 0.1354 for 2957 observed reflections with I 〉 2σ（I）. The thermogravimetric analysis （TGA） and fluorescent measurement have been done. The structure of compound 1 is a 3D open framework with 32-atom channels.
基金This research was supported by the State Key Laboratory of Structural Chemistry, the Chinese Academy of Sciences (CAS), the National Science and Technology of China (001CB1089), the NNSFC (20273073, 20333070, 90206040) and NSF of Fujian Province (2005HZ01-1, 2004HZ01-1, 2003J042 and 2004J041)
文摘One new Ni（Ⅱ） complex [Ni（H2L）]Cl（H2O）3 based on one in-situ synthesized Schiff base ligand H3L （H3L = bis（benzyl-2-pyridylidene）-diaminoguanidine） was prepared and structurally characterized by single-crystal X-ray diffraction method. The complex crystallizes in the monoclinic system, space group C2/c with a = 27.944（7）, b = 7.7405（19）, c = 25.999（7） ,A, β = 115.545（2）°, V = 5074（2） A^3, Mr = 566.69, Z = 8, Dc = 1.484 g/cm^3, F（000） = 2352,μ（MoKα） = 0.912 mm^-1, R = 0.0594 and wR = 0.1477 for 5145 observed reflections （1 〉 2σ（I））. The complex exhibits one mononuclear structure in which the Ni（Ⅱ） atom adopts a [NiN4] pseudo-planar square geometry. Interestingly, along the b axis, each two neighboring [Ni（H2L）]^＋ units by an inverse center form pairs of molecules through the intermolecular benzene-pyridine π…π interactions.
文摘The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.
基金the National Science Foundation of China(21773243,21973095)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB20010200)for financial support。
文摘We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2);n=1,3[PF6]_(2);n=5,4[PF6]_(2)) by using a mononuclear complex[PY5Me_(2)Ru(μ-CN)][PF_(6)](1) as the precursor.All the three complexes have been fully characterized by including single-crystal X-ray diffraction analysis.The one-electron oxidation complexes 2^(3+),3^(3+) and 4^(3+) obtained in situ all show a MMCT absorption band in the visible range.The MMCT energy increases as the redox potential of the N-terminal fragments decreases,and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases,supported by the TDF/TDDFT calculations.
基金the National Science Foundation of China(21773243,21973095)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB20010200)for financial support。
文摘To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer(MMCT)properties in similar mixed-valence(MV)complexes,a series of binuclear organometallic complexes,MeCp(dppe)RuCNFeCl_(3)(1),MeCp(PPh_(3))_(2)RuCNFeCl_(3)(2),Cp^(*)(dppe)FeCNFeCl_(3)(3),Cp^(*)(dppe)RuCNFeCl_(3)(4)and Cp^(*)(PPh_(3))_(2)RuCNFeCl_(3)(5),have been synthesized and characterized.The electronic absorptions of these complexes show the presence of MMCT properties between RuⅡ or FeⅡ and FeⅢ ions,strongly supported by the theoretical calculations.With increasing electron-donating ability of ligands(PPh3>dppe,Cp^(*)>MeCp)at donor site,the MMCT absorption bands are red-shifted,which expresses in the sequence of absorption bands with 1(500 nm),4(536 nm),2(542 nm),5(580 nm)from high-energy to low-energy.Meanwhile,the MMCT absorption energy of 4(536 nm)is larger than that of 3(760 nm)due to the stronger electron-donating ability of FeⅡ than RuⅡ.Furthermore,these complexes belong to the Class Ⅱ systems according to the Robin and Day’s classification.
基金the National Natural Science Foundation of China(21773243,21973095)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20010200)。
文摘Three dinuclear cyanide-bridged complexes[Fe^(Ⅱ)(PY_(5)OMe_(2))CNM^(Ⅱ)(PY_(5)OMe_(2))](OTf)_(3) (M=Fe1,M=Co 2,M=Mn 3)(PY_(5)OMe_(2)=2,6-bis-((2-pyridyl)methoxymethane)pyridine OTf=CF_(3)SO_(3)^(-)) have been synthesized and characterized.Single-crystal diffraction analyses show these three dinuclear compounds are very similar in structure.The measured ν(CN) results for compounds 1~3 suggest that Mn^(2+) is electron-poorer than Fe^(2+) and Co^(2+).Meanwhile,the temperature dependence of magnetic susceptibilities of complexes 1~3 reveals that in these three complexes,all the cyanide-carbon coordinated Fe(Ⅱ) is low-spin,and Co(Ⅱ) for 2 and Mn(Ⅱ) for 3are both in a high-spin state through 2~400 K but the cyanide-nitrogen coordinated Fe(Ⅱ) for complex 1 exhibits spin crossover (SCO) behavior over 300 K and a hysteresis of 36 K in both cooling and heating modes.
