配合物{[Cu(hmtade)][Ni(dmit)2]}2·4DMSO的合成、表征及晶体结构

合成了配合物{[Cu(hmtade)][Ni(dmit)2]}2·4DMSO(1)(hmtade为5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四-4,11-二烯; dmit为1,3-二硫杂环戊二烯-2-硫酮-4,5-二硫醇; DMSO为二甲亚砜), 采用元素分析、红外光谱和紫外-可见光谱进行了表征, 并用X射线衍射法测定了晶体结构. 该晶体属于单斜晶系, P21/n空间群; 晶胞参数: a=1.49952(6) nm, b=1.77229(7) nm, c=3.1275(1) nm, β=102.442(1)°, V=8.1163(5) nm3, Dc=1.558 Mg/m3, Z=8, F(000)=3944, μ(Mo Kα)=1.637 mm-1, S=1.016, (Δ/σ)max=0.001, R1=0.0673, wR2 =0.1672[I>2σ(I)]. 晶体结构研究表明, 配合物{[Cu(hmtade)]·[Ni(dmit)2]}2·4DMSO包含2个[Cu(hmtade)][Ni(dmit)2]子单元. 每个子单元中, 1个dmit中的1个S原子与Cu及Ni配位, 形成异双核Cu—Ni配合物. 其中Cu(Ⅱ)为五配位的四方锥构形, Cu—N键长在0.1949(5)~0.2007(4) nm范围内, Cu—S键长分别为0.28913(18)和0.28952(18) nm; 配阴离子[Ni(dmit)2]2-为畸变四方形, Ni—S键长在0.21729(16)~0.21905(17) nm范围内. 溶剂分子DMSO与配体hmtade形成了N—H…O氢键. 通过分子内S…S和S…H短接触形成了二聚体, 二聚体之间通过S…S短接触形成一维链状结构, 并通过S…S, S…H和C…H短接触进一步形成二维和三维结构.     

含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫代甲酸)合镍负离子加合物的合成、表征和[Ni(hmtade)][Ni(cdc)_2]的晶体结构

合成了七个含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫代甲酸)合镍负离子的加合物[ML][Ni(cdc)_2](cdc=N-氰基亚胺基二硫代甲酸根;L=hmtade,hmta,dmtade,tmtate;M=Cu,Ni,Zn),通过元素分析、红外光谱、电子光谱、磁化率和顺磁共振谱对加合物结构进行了表征.测定了[Ni(hmtade)][Ni(cdc)_2」的晶体结构,其晶体属单斜晶系,C2/c空间群,晶胞参数:a=1.1883(2),b=1.1753(2),c=2.0482(4)nm.α=90°,β=100.19(1)°,r=90°.V=2.8154nm~3,M_r=630.19.D_x=1.482g/cm~3,Z=4.对正负离子间的相互作用进行了讨论.     

三元配合物[Cu(hmta){SSP(OC6H11)2}2]的合成、谱学性质与晶体结构

合成了含饱和四氮杂大环hmta(hmate=meso-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷)和O,O'-二环己基二硫代磷酸的铜(Ⅱ)的三元配合物,通过元素分析、摩尔电导、红外光谱、1H核磁共振谱和电子光谱对其进行了表征,并用单晶x-ray衍射法测定了它的晶体结构.配合物属三斜晶系,空间群为P-1,晶胞参数为a=8.174(2)A,b=10.381(3)(A),c=15.419(3)(A),α=101.59(2)°,β=93.34(2)°,γ=103.76(2)°,V=1237.3(6)(A)3,Z=2,Dc=1.219mg/cm3,F(000)=477,μ(MoKα)=0.714mm-1,最终偏离因子(I＞2σ(I))R=0.0382,wR=0.0991,相应的可观测反射数为2763.测定结果表明配合物中的配体(C6H11)2PSS-为单齿配体,金属铜离子与(C6H11)2PSS-的S(2)原子和hmta的N原子形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性;同时晶胞中配合物的两配体之间形成了两种N-H…S氢键.     

含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫甲酸)合镍负离子加合物的合成、表征和[Ni(hmtade)][Ni(cdc)2]的晶体结构

合成了七个含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫代甲酸)合镍负离子的加合物[ML][Ni(cdc)2](cdc=N-氰基亚胺基二硫代甲酸根; L=hmtade,hmta, dmtade, tmtate; M=Cu, Ni, Zn), 通过元素分析、红外光谱、电子光谱、磁化率和顺磁共振谱对加合物结构进行了表征。测定了[Ni(hmtade)][Ni(cdc)2]的晶体结构, 其晶体属单斜晶系, C2/c空间群, 晶胞参数: a=1.1883(2), b=1.1753(2),c=2.0482(4)nm, α=90°, β=100.19(1)°, γ=90°,V=2.8154nm^3, Mr=630.19, Dx=1.482g/cm^3, Z=4, 对正负离子间的相互作用进行了讨论。     

含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫甲酸)合镍负离子加合物的合成、表征和[Ni(hmtade)][Ni(cdc)2]的晶体结构

合成了七个含四氮杂十四元大环配体过渡金属配正离子与双(N-氰基亚胺基二硫代甲酸)合镍负离子的加合物[ML][Ni(cdc)2](cdc=N-氰基亚胺基二硫代甲酸根; L=hmtade,hmta, dmtade, tmtate; M=Cu, Ni, Zn), 通过元素分析、红外光谱、电子光谱、磁化率和顺磁共振谱对加合物结构进行了表征。测定了[Ni(hmtade)][Ni(cdc)2]的晶体结构, 其晶体属单斜晶系, C2/c空间群, 晶胞参数: a=1.1883(2), b=1.1753(2),c=2.0482(4)nm, α=90°, β=100.19(1)°, γ=90°,V=2.8154nm^3, Mr=630.19, Dx=1.482g/cm^3, Z=4, 对正负离子间的相互作用进行了讨论。     

新型C~n[M(dmit)~2]类导电配位化合物的研究

首次将不饱和杂原子环状阳离子(N-甲基吡啶阳离子、N-甲基喹啉阳离子和N-甲基苯并噻唑阳离子)及三甲基苯基铵阳离子引入[M(dmit)~2]^n^-体系制备得到了6个新型的导电配位化合物C~n[M(dmit)~2](M=Ni,Pd,Pt,n=2,1)。对这些新化合物进行了组成和结构的测定,研究了它们的IR,UV,ESR和XPS,测定了变温磁化率和室温导电率。结果表明,外部阳离子的大小和形状会影响阴离子部分[M(dmit)~2]^n^-的荷电量以及电荷分布,从而导致配合物性能的改变,说明外部阳离子可以通过另外一种方式来影响配合物的电性能。     

含四氮杂大环的双(O,O'-二(2-苯乙基)二硫代磷酸根)合镍(II)或铜(II)配合物的合成和晶体结构

合成了含四氮杂大环hmta(hmta = meso-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷 )和O,O-二(2-苯乙基)二硫代磷酸根的配合物 [Ni(hmta){SSP(OCH2CH2Ph)2}2] 1和 [Cu(hmta){SSP(OCH2CH2Ph)2}2] 2 , 并测定了它们的晶体结构。配合物1属单斜晶系,空间群为P21/c,晶胞参数为: C48H72N4O4P2S4Ni, a = 9.827(3), b = 19.430(6), c = 13.932(3) ? b = 99.99(2), Mr = 1017.99, V = 2620(1) 3, Z = 2, Dc = 1.285 g/cm3, = 0.635 mm-1, F(000) = 1076, 最终的偏离因子为R = 0.0434, wR = 0.1078, 相应的可观测反射数为2306; 配合物2属单斜晶系, 空间群为P21/c, 晶胞参数为: C48H72N4O4P2S4CuO25, a = 9.730(4), b = 19.513(4), c = 14.031(3) ? b = 99.97(3), Mr = 1022.82, V = 2624 (1) 3, Z = 2, Dc = 1.295 g/cm3, = 0.681 mm-1, F(000) = 1086, 最终的偏离因子为R = 0.0465, wR = 0.1222, 相应的可观测反射数为2492。结构测定表明:两配合物中的配体 (PhCH2CH2O)2PS2-均为单齿配体,金属离子与硫和氮形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性; 同时晶胞中配合物的两配体之间形成了2种N-H贩稴氢键。     

四氮大环和O,O''''-二苯基二硫代磷酸铜/镍配合物的谱学性质与[Cu(hmta)·{SSP(Oph)2}2]的晶体结构

合成了含四氮杂大环hm ta(hm ta=5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷)和O,O’-二苯基二硫代磷酸的配合物[M(hm ta).SSP(OPh)2 2)](M=Cu(Ⅱ),1;N i(Ⅱ),2),通过元素分析、红外光谱1、H核磁共振谱、电子光谱和差热分析对其进行了表征,并用X-和射线衍射法测定了1的晶体结构。配合物1属单斜晶系,空间群为P21/n,晶胞参数为:a=9.026(2),b=21.610(6),c=11.736(3),β=105.65(2)°,V=2204.2(10)3,Z=4,Dc=1.372g/cm-3,F(000)=958,μ(MoKα)=8.01 cm-1,S=0.915,(Δ/σ)max=0.002。最终偏离因子(I>2σ(I)),R=0.0391,wR=0.0937,相应的可观测反射数为1914。测定结果表明:配合物中的(PhO)2PSS-为单齿配体,金属离子与配体(PhO)2PSS-的疏和hm ta的氮形成了变型的八面体,配合物具有中心对称性;两配体之间形成了N-H…S氢键。     

新型氮功能化大环配体的合成与表征

合成了新型氮功能化大环配体内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇-二乙酸乙酯(TETADE);内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇,N＇,N＇＇,N＇＇＇-四乙酸乙酯(TETADE);内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇-二乙酸(TETADA);内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇,N＇,N＇＇＇-四乙酸(TETATA)和内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇-二异羟肟酸(TETAD-HA).均通过元素分析、IR,1H NMR和MS表征.     

含四氮杂大环的双(O,O''''-二(2-苯乙基)二硫代磷酸根)合镍(II)或铜(II)配合物的合成和晶体结构

合成了含四氮杂大环hmta(hmta = meso-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷 )和O,O-二(2-苯乙基)二硫代磷酸根的配合物 [Ni(hmta){SSP(OCH2CH2Ph)2}2] 1和 [Cu(hmta){SSP(OCH2CH2Ph)2}2] 2 , 并测定了它们的晶体结构。配合物1属单斜晶系,空间群为P21/c,晶胞参数为: C48H72N4O4P2S4Ni, a = 9.827(3), b = 19.430(6), c = 13.932(3) ? b = 99.99(2), Mr = 1017.99, V = 2620(1) 3, Z = 2, Dc = 1.285 g/cm3, = 0.635 mm-1, F(000) = 1076, 最终的偏离因子为R = 0.0434, wR = 0.1078, 相应的可观测反射数为2306; 配合物2属单斜晶系, 空间群为P21/c, 晶胞参数为: C48H72N4O4P2S4CuO25, a = 9.730(4), b = 19.513(4), c = 14.031(3) ? b = 99.97(3), Mr = 1022.82, V = 2624 (1) 3, Z = 2, Dc = 1.295 g/cm3, = 0.681 mm-1, F(000) = 1086, 最终的偏离因子为R = 0.0465, wR = 0.1222, 相应的可观测反射数为2492。结构测定表明:两配合物中的配体 (PhCH2CH2O)2PS2-均为单齿配体,金属离子与硫和氮形成了六配位的拉长的八面体配合物,配合物分子具有中心对称性; 同时晶胞中配合物的两配体之间形成了2种N-H贩稴氢键。     

Towards Single-component Molecular Conductor [Ni(dmit)_2] by Charge Disproportionation:2[Ni(dmit)_2]~(-0.5)[Ni(dmit)_2]+[Ni(dmit)_2]~-

It was commonly thought that a molecular conductor or semiconductor should be composed of at least two components to make the conducting component in partially charged state. However, this idea became questionable by the recent report of the single-component molecular conductor [Ni(tmdt)2]1 as well as several reports about single-component molecular semiconductors such as [Ni(ptdt)2]2 and [Ni(C10H10S8)2]3. In fact, as early as 1985, [Ni(dmit)2] as a by-product in synthesizing TTF[Ni(dmit…     

金属有机自由基离子盐[Fe(CpMe)2][M(dmit)2]和[FeCp(Tol)]n[M(dmit)2]的合成和固体导电性质

报道了6个新的含均同或混合茂铁阳离子和[M(dmit)₂]阴离子的金属有机自由基离子盐类化合物[Fe(CpMe)₂]IM(dmit)₂]和[FeCp(Tol)],[M(dmit)₂]的合成和鉴定,测定了化合物的电导率,讨论了化合物的结构对电导率的影响,发现[Fe(CpMe)₂][M(dmit)₂]的室温电导率比相应的[M(mnt)₂]阴离子盐要高37个数量级.     

分子导体(PyH)[Ni(dmit)_2]_2的合成、结构与导电性

合成了一种新的导电分子晶体(PyH)[Ni(dmit)_2]_2 (Py = pyridine, dmit = (C_3S_5)~(2-) = 4,5-dimercapto-1,3-dithiole-2-thione)，用元素分析、红 外光谱对其进行了表征，并用四圆X射线衍射方法确定了结构，该晶体属于三斜晶 系，P-1空间群；晶胞参数为: a = 0.59227(4) nm，b = 0.82279(6) nm, c = 1. 67535(9) nm, α = 90.233(5)°, β = 92.107(5)°, γ = 104.654(6)°; V = 0.78925(9) nm~3, Z = 1. (PyH)[Ni(dmit)_2]_2晶体中，导电组元[Ni(dmit)_2] ~(-0.5) 沿b轴方向形成具有二聚体结构的柱状堆积，在(001)面形成以肩并肩分子 间的S…S强相互作用为特征的二维导电层，这种二维导电层上的室温电导率为0. 13 Ω~(-1)·cm~(-1)，在c轴方向，(PyH)~+与[Ni(dmit)_2]~(-0.5)之间除库仑作 用外，还存在N-H…S，C-H…S氢键相互作用。单晶(001)面上变温电阻的测定结果 表明，在90 K到室温的温度范围内，(PyH)[Ni(dmit)_2]_2具有半导体导电行为， 导电激活能为0.15 eV。     

Towards Single-component Molecular Conductor [Ni（dmit）2 ] by Charge Disproportionation： 2[Ni（dmit）2]^0.5→[Ni（dmit）2 ]＋ [Ni（dmit）2]^-

A new method of synthesizing single-component molecular conductor [Ni(dmit)2] bythe reaction 2(Me4N)[Ni(dmit)2]2→ [Ni(dmit)2] (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2]exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.     

THE CRYSTAL STRUCTURE OF BEDT-TTF[Pd(dmit)_2] (H_2dmit=4,5-dimercapto-1,3-dithiole-2-thione)

<正> C16H8PdS18, Mr=984.6, triclinic, Pl, a=6.6889(20), b=7.3824(21), c=15.0945(38)A; α=92.098(23)°,β=97.958(22)°, r=109.269(22)°, V=694.14(33)A3, Z=1; μ(MoKα)=19.68 cm-1. F(000)=437.98, room temperature, R=0.042, Rw=0.041 for 1865 independent diffractions. Planar BEDT-TTF and Pd(dmit)a stack along b axis separately. The separation between BEDT-TTFs is 6.74A, that between Pd(dimt)a planes 6.53A. This feature of BEDT-TTF[Pd(dimt)2] stacking may be used to explain the semiconducting character of the title compound.     

ESR Investigation of Single Crystal of (Bu_4N)_2[Cu/Pd(dmit)_2]

By incorporating (Bu4N)2[Cu(dmit)2] with the diamagnetic host complex (Bu4N)2[Pd (dmit)2], single crystal of (Bu4N)2[Cu/Pd(dmit)2] is obtained. Its ESR spectra of various orientations are recorded. The principal values of g and A tensors and their direction cosines are computed using a least-squares fitting procedure, and based on which the molecular orbital of unpaired electron in [Cu(dmit)2]2- is described. The essence of the two magnetically non-equivalent sites is also revealed.     

Electrochemical Behavior and Redox Switch Properties of [Zn(dmit)_2]~(2-)

The redox behavior of [Zn(dmit)2]2- and its electrodeposited film were investigated by cyclic voltammetry, and the Ⅰ-Ⅴ properties of the electrodeposited film were measured. The results show that [Zn(dmit)2]2- possesses good redox switch properties which exhibit good repeatability. It could be considered as a new material for molecular switch and memory.     

M(R-dmet)2] bis(1,2-dithiolenes): a promising new class intermediate between [M(dmit)2] and [M(R,R'-timdt)2] (M = Ni, Pd, Pt)

We report the first examples of metal dithiolenes belonging to the class [M(R-dmet)(2)] [R-dmet = formally monoreduced N-substituted thiazolidine-2,4,5-trithione; R = Et, M = Ni (1), Pd (2), Pt (3)]. A comparative spectroscopic, electrochemical, and density functional theory theoretical investigation indicates that [M(R-dmet)(2)] complexes show features intermediate between those of the dithiolenes belonging to the previously reported classes [M(R,R'-timdt)(2)] and [M(dmit)(2)] (R,R'-timdt = formally monoreduced N,N'-disubstituted imidazolidine-2,4,5-trithione; dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). UV-vis-near-IR spectroscopy and cyclic voltammetry/differential pulsed voltammetry measurements performed on 1 and 3 proved that the new dithiolenes are stable as neutral, monoanionic, and bianionic species and feature a near-IR electrochromic absorption falling at about 1000 and 1250 nm for neutral and monoanionic species, respectively.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

弱相互作用构筑的二维、三维冠醚配合物{[K(18-C-6)2(C2H4Cl2)}[Ni(dmit)2]2和[K(18-C-6)][Ni(dmit)2]的合成与结构

研究了18－冠－6与NiCl·6H2O,K2dmit(dmit=4,5-dimercapto-1,3-dithiole- 2-thione,C3S5^2－）在不同溶剂中反应生成的两个标题配合物{[K(18-C-6)]2 (C2H4Cl2)}[Ni(dmit)2]2（1）和[K(18-C-6)][Ni(dmit)2](2)。通过元素分析、红 外光谱、单晶X射线衍射进行了表征。1和2均属三斜晶系,空间群P1^-.1的晶体学 数据：a=1.0272(2)nm,b=1.2282(3)nm,c=1.4205(3)nm,α=113.473(3)°,β=90. 609(3)°,γ=91.439(3)°,V=1.6430(6)nm^3,Z=2,F（000)=876,R1=0.0503。2的 晶体学数据：a=0.8502(2)nm,b=1.2178(4)nm,c=1.5118(4)nm,α=86.454(5)°,β =77.734(5)°,γ=85.364(5)°,V=1.5228(8)nm^3,Z=2,F(000)=774,R1=0.0565。配 合物1,2分别通过K…S,K…Cl,S…S和K…S,S…S弱相互作用形成二维、三维网状 结构。