Reaction of [PPh_4][(η 5-C_5Me_5)WS_3] with CuI,CuBr and bis^(diphenylphosphino)methane (dppm) (molar ratio=1∶2∶1∶1) in MeCN gave rise to [PPh_4][(η 5-C_5Me_5)WS_3(CuBr)(CuI)_2-(μ-dppm)] (1) in high yield. Com...Reaction of [PPh_4][(η 5-C_5Me_5)WS_3] with CuI,CuBr and bis^(diphenylphosphino)methane (dppm) (molar ratio=1∶2∶1∶1) in MeCN gave rise to [PPh_4][(η 5-C_5Me_5)WS_3(CuBr)(CuI)_2-(μ-dppm)] (1) in high yield. Compound 1 crystallizes in the monoclinic,space group P2_1/n with lattice parameters:a=1.2906(4) nm, b=1.5006(8) nm,c=3.1484(6) nm,β= 92.12(2)°,V=6.093(3) nm 3,Z=4. The structure of the anion of 1 contains an incomplete WS_3Cu_3 cubane-like core in which two CuI units are bridged by a dppm ligand. The W—Cu distances vary in the range of 0.2644(1)—0.2793(1) nm. The optical limiting (OL) properties of 1 in MeCN were measured with the laser pulse-width of 12-ns at 532 nm,and the nanosecond OL effect may be due to the reverse saturable absorption (RSA) related to the excited triplet states.展开更多
The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the ...The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2（dmpzm）2]·DMF（2·DMF）.Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2（MeCN）0.5 crystallizes in triclinic,space group P1-with a = 11.4552（5）,b = 11.6735（3）,c = 16.2278（9） ,α = 99.537（9）,β = 101.986（2）,γ = 118.464（13）o,V = 1775.5（3）3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193（2） K,C24H35Cu3IN9OS3W,Mr = 1063.22,F（000） = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145（4）,b = 11.464（2）,c = 7.7370（15） ,V = 1964.2（6）3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193（2） K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F（000） = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2（MeCN）0.5 consists of one CuI and two [Cu（dmpzm）]＋ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.展开更多
The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was dete...The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) ? V = 7054.6(8) 3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, m (Mo Ka) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one [(h5-C5Me5)WS3(CuBr)3]22- dianion, one [Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (h5-C5Me5)WS3(CuBr)3 fragments connected by a pair of CuBrCu bridges to form a double incomplete-cubane structure. The range of WCu distance is 2.657(1)~2.677(2) ?in the W2Cu6S6 cluster core.展开更多
Reaction of (NH4)2WOS3 with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster WOS3Cu3I(4-bpy)3·0.25EtOH. This compound was characterized by elementary analysis, IR, 1H NMR, TGA,...Reaction of (NH4)2WOS3 with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster WOS3Cu3I(4-bpy)3·0.25EtOH. This compound was characterized by elementary analysis, IR, 1H NMR, TGA, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2/c with a=2.220 9(2) nm, b=1.364 66(11) nm, c=2.490 6(2) nm, β=104.953(2)°, V=7.292 9(12) nm3, Z=4. The title compound may be viewed as having a half-open cubane-like structure in which three Cu(4-bpy)+ units are linked by a triply-bridging WOS32- unit and a doubly-bridging iodine atom. CCDC: 266412.展开更多
Reaction of a preformed cluster [｛(η5-C5Me5)WS3｝3Cu7(MeCN)9](PF6)4 (1) in MeCN with LiCl and PPh3 gave rise to a tetranuclear cationic cluster [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl](PF6) (2). The title compound 2 was char...Reaction of a preformed cluster [｛(η5-C5Me5)WS3｝3Cu7(MeCN)9](PF6)4 (1) in MeCN with LiCl and PPh3 gave rise to a tetranuclear cationic cluster [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl](PF6) (2). The title compound 2 was char- acterized by elementary analysis, IR, UV-Vis, 1H NMR, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P21/c with a=1.7998(4) nm, b=2.0836(4) nm, c=1.9135(4) nm, β=113.63(3)°, V=6.574(3) nm3, Z=4. The cluster cation [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl]+ of 2 contains a strongly distorted, cubane-like structure [WS3Cu3Cl] in which one Cl weakly fills into the void of the nido-like [WS3Cu3] fragment with three relatively long Cu-Cl distances. CCDC: 270415.展开更多
The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniq...The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.展开更多
The complex Na2 [CrW3O4(O2CCH3)8]2·H2O (Mr = 2343. 80) crystallizes in monoclinic, space group P21/n with a=11. 206 (4 ), b=18. 016 (9), c=14. 465 (5) A, β=98. 00(3)°, V=2891. 9 A, Z=2, Dc=2. 69 g/cm3, F(00...The complex Na2 [CrW3O4(O2CCH3)8]2·H2O (Mr = 2343. 80) crystallizes in monoclinic, space group P21/n with a=11. 206 (4 ), b=18. 016 (9), c=14. 465 (5) A, β=98. 00(3)°, V=2891. 9 A, Z=2, Dc=2. 69 g/cm3, F(000) =2168. Final R= 0.043, Rw=0.049 for 3144 independent reflections with I>3σ(I).The complex anion contains two W3O4 core which were connected by two Cr atomsthrough four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atomsand the W atoms is coordinated by six oxygen atome. The amons are linked by Na+cations to form one-dimensional infinite chain structure. The infrared spetrum of thecompound has been measured and rationally assigned.展开更多
The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the '...The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the 'loose' ligands are determined. The crystallographic data of the cluster compounds with [W_3S_4]￣(4+) and [W_3CuS_4]￣(5+) cores are compared and their UV-Vis spectra are firstly reported. Thus, the 'quasi-aromaticity' of the [W_3S_4]￣(4+) core of these cluster compounds is discussed.展开更多
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 2 710 3 6) ,theNaturalScienceFoundationoftheEducationCommitteeofJiangsuProvince (No .0 2KJB15 0 0 0 1) ,StateKeyLabofCoordinationChemistryofNanjingUniversity ,andtheScientificResearchF
文摘Reaction of [PPh_4][(η 5-C_5Me_5)WS_3] with CuI,CuBr and bis^(diphenylphosphino)methane (dppm) (molar ratio=1∶2∶1∶1) in MeCN gave rise to [PPh_4][(η 5-C_5Me_5)WS_3(CuBr)(CuI)_2-(μ-dppm)] (1) in high yield. Compound 1 crystallizes in the monoclinic,space group P2_1/n with lattice parameters:a=1.2906(4) nm, b=1.5006(8) nm,c=3.1484(6) nm,β= 92.12(2)°,V=6.093(3) nm 3,Z=4. The structure of the anion of 1 contains an incomplete WS_3Cu_3 cubane-like core in which two CuI units are bridged by a dppm ligand. The W—Cu distances vary in the range of 0.2644(1)—0.2793(1) nm. The optical limiting (OL) properties of 1 in MeCN were measured with the laser pulse-width of 12-ns at 532 nm,and the nanosecond OL effect may be due to the reverse saturable absorption (RSA) related to the excited triplet states.
基金Supported by the National Natural Science Foundation of China (No. 20525101,20801038) "Soochow Scholar" Program of Suzhou University
文摘The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2（dmpzm）2]·DMF（2·DMF）.Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2（MeCN）0.5 crystallizes in triclinic,space group P1-with a = 11.4552（5）,b = 11.6735（3）,c = 16.2278（9） ,α = 99.537（9）,β = 101.986（2）,γ = 118.464（13）o,V = 1775.5（3）3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193（2） K,C24H35Cu3IN9OS3W,Mr = 1063.22,F（000） = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145（4）,b = 11.464（2）,c = 7.7370（15） ,V = 1964.2（6）3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193（2） K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F（000） = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2（MeCN）0.5 consists of one CuI and two [Cu（dmpzm）]＋ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.
基金supported by Suzhou University(XQ109020 and Q4109927)
文摘The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) ? V = 7054.6(8) 3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, m (Mo Ka) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one [(h5-C5Me5)WS3(CuBr)3]22- dianion, one [Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (h5-C5Me5)WS3(CuBr)3 fragments connected by a pair of CuBrCu bridges to form a double incomplete-cubane structure. The range of WCu distance is 2.657(1)~2.677(2) ?in the W2Cu6S6 cluster core.
文摘Reaction of (NH4)2WOS3 with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster WOS3Cu3I(4-bpy)3·0.25EtOH. This compound was characterized by elementary analysis, IR, 1H NMR, TGA, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2/c with a=2.220 9(2) nm, b=1.364 66(11) nm, c=2.490 6(2) nm, β=104.953(2)°, V=7.292 9(12) nm3, Z=4. The title compound may be viewed as having a half-open cubane-like structure in which three Cu(4-bpy)+ units are linked by a triply-bridging WOS32- unit and a doubly-bridging iodine atom. CCDC: 266412.
文摘Reaction of a preformed cluster [｛(η5-C5Me5)WS3｝3Cu7(MeCN)9](PF6)4 (1) in MeCN with LiCl and PPh3 gave rise to a tetranuclear cationic cluster [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl](PF6) (2). The title compound 2 was char- acterized by elementary analysis, IR, UV-Vis, 1H NMR, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P21/c with a=1.7998(4) nm, b=2.0836(4) nm, c=1.9135(4) nm, β=113.63(3)°, V=6.574(3) nm3, Z=4. The cluster cation [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl]+ of 2 contains a strongly distorted, cubane-like structure [WS3Cu3Cl] in which one Cl weakly fills into the void of the nido-like [WS3Cu3] fragment with three relatively long Cu-Cl distances. CCDC: 270415.
文摘The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.
文摘The complex Na2 [CrW3O4(O2CCH3)8]2·H2O (Mr = 2343. 80) crystallizes in monoclinic, space group P21/n with a=11. 206 (4 ), b=18. 016 (9), c=14. 465 (5) A, β=98. 00(3)°, V=2891. 9 A, Z=2, Dc=2. 69 g/cm3, F(000) =2168. Final R= 0.043, Rw=0.049 for 3144 independent reflections with I>3σ(I).The complex anion contains two W3O4 core which were connected by two Cr atomsthrough four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atomsand the W atoms is coordinated by six oxygen atome. The amons are linked by Na+cations to form one-dimensional infinite chain structure. The infrared spetrum of thecompound has been measured and rationally assigned.
文摘The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the 'loose' ligands are determined. The crystallographic data of the cluster compounds with [W_3S_4]￣(4+) and [W_3CuS_4]￣(5+) cores are compared and their UV-Vis spectra are firstly reported. Thus, the 'quasi-aromaticity' of the [W_3S_4]￣(4+) core of these cluster compounds is discussed.
