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 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
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
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.
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.
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.
