新型产氢催化剂的合成及其光催化产氢性能研究

<正>太阳能光解水制氢被认为是人类解决能源危机的有效途径之一,高效稳定廉价产氢催化剂的研究一直是太阳能光解水制氢领域的难点和热点。本论文设计合成了多种类型的产氢催化剂,在多组分体系中研究了催化剂活性与结构间的依赖关系。主要研究结果如下:1.设计合成了两种双核Rh配合物[Rh2(bpy)2(μ-O2CCH3)2]2+和[Rh2(phen)2(μ-O2CCH3)2]2+,     

水溶性四(p-磺酸钠苯基)金属卟啉配合物的合成、光谱性质及催化三氯苯酚的氧化脱氯反应

通过四苯基卟啉(H2TPP)和浓硫酸发生磺化反应及其金属化, 控制反应体系pH并利用透析法纯化, 高效合成了水溶性四(对磺酸钠苯基)卟啉(H2TPPS)及其金属配合物(FeTPPS和ZnTPPS); 采用UV-Vis、荧光、1H NMR和FTIR等光谱手段表征及研究了水溶性卟啉的结构及性质. 结果表明, 磺酸根离子的存在增强了卟啉分子间的π-π作用, 从而使H2TPPS及其金属配合物的分子间聚合作用增强. 研究了FeTPPS对2,4,6-三氯苯酚(TCP)催化氧化脱氯反应, 结果表明, FeTPPS/H2O2催化体系对TCP具备很好的催化氧化脱氯性能, 2,6-二氯对苯醌的转化数达到了766.     

利用静电吸引作用提高光催化放氢效率

本文设计合成了两个分别带正电荷和负电荷的Ir(Ⅲ)配合物[Ir(ppy)₂(bpy)]⁺(ppy=2-苯基吡啶,bpy=2,2′-联吡啶)和[Ir(ppy)₂(pbs)]^-(pbs=1,10-菲啰啉-4,7-二苯磺酸钠)作为光敏剂,以[Co(bpy)₃]²⁺为放氢催化剂,比较了Ir(Ⅲ)配合物的光催化放氢效率.发现带负电荷的Ir(Ⅲ)配合物具有更高的光催化放氢效率,带负电荷光敏剂和带正电荷催化剂间的静电吸引可能对放氢效率的提高起到了重要作用.     

双吡啶酰腙Schiff碱HgⅡ/Cd(Ⅱ)配合物的合成及其对甲醇蒸气的吸附

合成了双吡啶酰腙Schiff碱配体(L),并采用核磁共振氢谱、质谱、红外光谱和元素分析等手段对其结构进行了表征。进一步采用溶剂挥发法合成了2个配合物{[Cd(L)_2Cl_2]·2DMF·6H_2O}n (1)和[Hg(L)Cl_2]n (2)。通过X射线单晶衍射技术测定了配体及2个配合物的单晶结构,并对配合物的热稳定性及其在常温下对甲醇蒸气的吸附进行了考察。实验结果表明,2个配合物均为1D配位聚合物,配合物1对甲醇蒸气有较好的吸附能力。     

正方平面顺二羰基(二齿N-配体)铑(Ⅰ)阳离子配合物的XPS研究

用XPS研究了十五个[Rh(CO)_2(che1l]BPh_4系列配合物的结构、配位形式及电荷分布、结果表明,配位时电荷转移的行径为:(1)Rh←CO;(2)Rh←N;(3)[Rh(CO)_2(chel)~+→B.同时,每一配合物铑原子的价电子密度与配体有关。     

席夫碱类混价七核锰金属配合物的合成、表征及磁性

以3-乙氧基水杨醛缩乙醇胺席夫碱(H2L)为配体合成了2个新的七核锰配合物[Na2MnⅡMnⅢ6O2(L)6(N3)4(CH3COO)2]·4DMF(1)和[Na2MnⅡMnⅢ6O2(L)6(SCN)4(CH3COO)2]·2DMF (2),并对它们进行红外分析、元素分析、热重分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为混价七核锰配合物,包含1个Mn2+和6个Mn3+。此外还研究了配合物1和2的磁学性质,磁性研究表明配合物1和2都表现出反铁磁作用。     

两个2,6-二氨基-3,5-二硝基吡嗪-1-氧化物含能配合物的合成、晶体结构及催化性能(英文)

合成了2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105)2种含能配合物[Cu4O2(C4N6O5H2)2(CH3COO)2(DMF)2]·DMF(1)((C4N6O5H2)2-为配体LLM-105失去2个H+)和[Co(C4N6O5H3)3]·7H2O(2)((C4N6O5H3)-为LLM-105失去1个H+),用X射线单晶衍射法测定了其分子结构。配合物1属正交晶系,空间群为Pbca,配合物2属三斜晶系,空间群为R3。用DSC,TG-DTG技术对配体和2个配合物的热分解进行了研究。用Kissinger法和Ozawa-Doyle法对配合物热分解过程中放热峰的表观活化能进行了计算。同时研究了2种配合物对AP热分解催化效果的影响,结果表明,2种配合物使AP的高温分解峰温分别提前117.42和71.85℃,分解放热量增加1 916.97和1 433.76 J·g-1,对AP热分解具有非常显著的催化效果。     

稀土配合物{La［o-C6H4(NO2)(CO2)］3·(DMF)2}2的晶体结构及其荧光性能

合成了一种新的双核倒反中心的稀土镧配合物{La［o-C6H4(NO2)(CO2)］3·(DMF)2}2. 通过元素分析、 核磁共振谱和红外光谱对配合物的组成和结构进行了表征,  用热重分析研究了该配合物的热稳定性,  用X射线单晶衍射法测定了其晶体结构. 镧配合物{La［o-C6H4(NO2)(CO2)］3·(DMF)2}2晶体属三斜晶系, 空间群P1,  晶胞参数a=1.902(2) nm, b=1.245 0(2) nm, c=1.298 7(2) nm, α=64.555(2)°, β=66.348(2)°, γ=71.920(2)°, V=1.569 5(5) nm3, Dc=1.658 Mg/m3, Z=2, μ=1.437 mm-1, F(000)=784. 配合物中有2个La(Ⅲ)被4个邻硝基苯甲酸的羧酸根的负氧离子桥联, 每个La(Ⅲ)的中心离子配位数为9,  配位原子分别来自于7个邻硝基苯甲酸的羧酸根的负氧离子和2个DMF的羰基氧原子. 化合物中的氢键和π…π堆积作用使其成为三维立体结构. 同时发现了标题化合物固体具有光致发光现象, 发光性能测试表明， 配合物具有很好的荧光性质.     

稀土配合物{La[o-C_6H_4(NO_2)(CO_2)]_3·(DMF)_2}_2的晶体结构及其荧光性能

合成了一种新的双核倒反中心的稀土镧配合物{La[o-C6H4(NO2)(CO2)]3.(DMF)2}2.通过元素分析、核磁共振谱和红外光谱对配合物的组成和结构进行了表征,用热重分析研究了该配合物的热稳定性,用X射线单晶衍射法测定了其晶体结构.镧配合物{La[o-C6H4(NO2)(CO2)]3.(DMF)2}2晶体属三斜晶系,空间群P1,晶胞参数a=1.902(2)nm,b=1.245 0(2)nm,c=1.298 7(2)nm,α=64.555(2),°β=66.348(2),°γ=71.920(2)°,V=1.569 5(5)nm3,Dc=1.658 Mg/m3,Z=2,μ=1.437 mm-1,F(000)=784.配合物中有2个La(Ⅲ)被4个邻硝基苯甲酸的羧酸根的负氧离子桥联,每个La(Ⅲ)的中心离子配位数为9,配位原子分别来自于7个邻硝基苯甲酸的羧酸根的负氧离子和2个DMF的羰基氧原子.化合物中的氢键和π…π堆积作用使其成为三维立体结构.同时发现了标题化合物固体具有光致发光现象,发光性能测试表明,配合物具有很好的荧光性质.     

水溶性卟啉光还原水产氢的研究

自1977年Lehn报道Ru(bPy)_3~(2+)-TEOA-Rh(bPy)_3~(3+)-Pt催化体系光解水放氢以来,以金属配合物为光敏剂光解水产氢的研究日趋活跃。这些光化学体系通常由光敏剂、电子给体、中继物和氧化还原催化剂四组分组成。为了有效地实现阳光分解水产氢,选择一个在可见光区有强吸收的光敏剂是十分重     

Chiral organometallic triangles with Rh-Rh bonds. 1. Compounds prepared from racemic cis-Rh2(C6H4PPh2)2(OAc)2

Reaction of racemic cis-Rh(2)(C(6)H(4)PPh(2))(2)(OAc)(2)(HOAc)(2) with excess Me(3)OBF(4) in CH(3)CN results in the formation of racemic cis-[Rh(2)(C(6)H(4)PPh(2))(2)(CH(3)CN)(6)](BF(4))(2).0.5H(2)O (1.0.5H(2)O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH(3)CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4'-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh(2)(C(6)H(4)PPh(2))(2)](3)(C(2)O(4))(3)(py)(6).6MeOH.H(2)O (2.6MeOH.H(2)O), [Rh(2)(C(6)H(4)PPh(2))(2)](3)(O(2)CC(6)H(4)CO(2))(3)(DMF)(6).6.5DMF.0.5H(2)O (3.6.5DMF.0.5H(2)O), and [Rh(2)(C(6)H(4)PPh(2))(2)](3)(O(2)CC(6)H(4)C(6)H(4)CO(2))(3)(py)(6).4.5CH(3)OH.0.75H(2)O (4.4.5CH(3)OH.0.75H(2)O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and (31)P NMR spectroscopy.     

水溶液中meso-四(4-磺苯基)卟啉二聚体的形成和伏安行为研究

本文研究了水溶液中meso-四(4-磺苯基)卟啉(TPPS)二聚体(Dimer)的各种影响因素和它的电化学性质。提出了二聚体的模型, 说明了水溶性金属卟啉(Cu^2+,Zn^2+, Mn^2+-TPPS)循环伏安图上的一对小尖峰是二聚体在汞电极上吸附还原和氧化的结果。     

Syntheses, structural characterization and properties of transition metal complexes of 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5',5'-(1,1'-biphenyl)-4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5',5'-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt)

The hydrothermal chemistry of a variety of M(II)SO(4) salts with the tetrazole (Ht) ligands 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5',5'-(1,1'-biphenyl)4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5',5'-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt) was investigated. In the case of Co(II), three phases were isolated, two of which incorporated sulfate: [Co(5)F(2)(dbdt)(4)(H(2)O)(6)]·2H(2)O (1·2H(2)O), [Co(4)(OH)(2)(SO(4))(bdt)(2)(H(2)O)(4)] (2) and [Co(3)(OH)(SO(4))(btt)(H(2)O)(4)]·3H(2)O (3·3H(2)O). The structures are three-dimensional and consist of cluster-based secondary building units: the pentanuclear {Co(5)F(2)(tetrazolate)(8)(H(2)O)(6)}, the tetranuclear {Co(4)(OH)(2)(SO(4))(2)(tetrazolate)(6)}(4-), and the trinuclear {Co(3)(μ(3)-OH)(SO(4))(2) (tetrazolate)(3)}(2-) for 1, 2, and 3, respectively. The Ni(II) analogue [Ni(2)(H(0.67)bdt)(3)]·10.5H(2)O (4·10.5H(2)O) is isomorphous with a fourth cobalt phase, the previously reported [Co(2)(H(0.67)bat)(3)]·20H(2)O and exhibits a {M(tetrazolate)(3/2)}(∞) chain as the fundamental building block. The dense three-dimensional structure of [Zn(bdt)] (5) consists of {ZnN(4)}tetrahedra linked through bdt ligands bonding through N1,N3 donors at either tetrazolate terminus. In contrast to the hydrothermal synthesis of 1-5, the Cd(II) material (Me(2)NH(2))(3)[Cd(12)Cl(3)(btt)(8)(DMF)(12)]·xDMF·yMeOH (DMF = dimethylformamide; x = ca. 12, y = ca. 5) was prepared in DMF/methanol. The structure is constructed from the linking of {Cd(4)Cl(tetrazolate)(8)(DMF)(4)}(1-) secondary building units to produce an open-framework material exhibiting 66.5% void volume. The magnetic properties of the Co(II) series are reflective of the structural building units.     

An Unusual Organometallic Supramolecule Composed of Chiral Dirhodium Units and Sulfato Bridging Ligands

A chiral supramolecular compound (H3O){[cis-Rh2((C6H5)2P(C6H4))2(SO4)- (DMF)]2(μ- OC2H5)}·6C2H5OH (1) has been synthesized and characterized by X-ray single-crystal analysis. Compound 1 crystallizes in monoclinic, space group C2/c with a = 26.752(3), b = 13.5868(16), c = 26.611(3) , β = 103.891(2)°, V = 9389.5(19) 3, Z = 4, C92H114N2O18P4Rh4, Mr = 2135.49, Dc = 1.511 g/cm3, F(000) = 4384 and μ(MoKα) = 0.870 mm-1. The final R = 0.0441 and wR = 0.1186 for 8283 observed reflections with I > 2σ(I) and R = 0.0567 and wR = 0.1290 for all data. The structure of the compound is unique. It contains two inherent chiral {cis-Rh2[(C6H5)2P(C6H4)]2}2+ units which are connected not only in the equatorial positions by two sulfato ligands, but also in two of their axial positions by a μ2 ethoxide anion. The remaining axial positions of Rh24+ units in 1 are occupied by the DMF molecules. The sulfato ligands act as μ4 tridentate bridges to connect the Rh24+ units. The Rh-Rh metal-metal bond distances are comparable to those in analogous dirhodium compounds.     

Various forms of linear dipyridyls in discrete rectangles, dinuclear rods, and one-dimensional networks containing (eta5-pentamethylcyclopentadienyl)rhodium(III)

[Cp*Rh(eta1-NO3)(eta2-NO3)] (1) reacted with pyrazine (pyz) to give a dinuclear complex [Cp*Rh(eta1-NO3)(mu-pyz)(0.5)]2.CH2Cl2(3.CH2Cl2). Tetranuclear rectangles of the type [Cp*Rh(eta1,mu-X)(mu-L)(0.5)]4(OTf)4(4a: X = N3, L = bpy; 4b: X = N3, L = bpe; 4c: X = NCO, L = bpy) were prepared from [Cp*Rh(H2O)3](OTf)2 (2), a pseudo-halide (Me3SiN3 or Me3SiNCO), and a linear dipyridyl [4,4'-bipyridine (bpy) or trans-1,2-bis(4-pyridyl)ethylene (bpe)] by self-assembly through one-pot synthesis at room temperature. Treating complex with NH4SCN and dipyridyl led to the formation of dinuclear rods, [Cp*Rh(eta1-SCN)3]2(LH2) (5a: L = bpy; 5b: L = bpe), in which two Cp*Rh(eta1-SCN)3 units are connected by the diprotonated dipyridyl (LH2(2+)) through N(+)-H...N hydrogen bonds. Reactions of complex 2 with 1-(trimethylsilyl)imidazole (TMSIm) and dipyridyl (bpy or bpe) also produced another family of dinuclear rods [Cp*Rh(ImH)3]2.L (6a: L = bpy; 6b: L = bpe). Treating 1 and 2 with TMSIm and NH4SCN (in the absence of dipyridyl) generated a 1-D chain [Cp*Rh(ImH)3](NO3)2 (7) and a 1-D helix [Cp*Rh(eta1-SCN)2(eta1-SHCN)].H2O (8.H2O), respectively. The structures of complexes 3.CH2Cl2, 4a.H2O, 4c.2H2O, 5b, 6a, 7 and 8.H2O were determined by X-ray diffraction.     

Novel binding interactions of the DNA fragment d(pGpG) cross-linked by the antitumor active compound tetrakis(mu-carboxylato)dirhodium(II,II)

Insight into the N7/O6 equatorial binding interactions of the antitumor active complex Rh(2)(OAc)(4)(H(2)O)(2) (OAc(-) = CH(3)CO(2)(-)) with the nucleotide 5'-GMP and the DNA fragment d(pGpG) has been obtained by one- (1D) and two-dimensional (2D) NMR spectroscopy. The lack of N7 protonation at low pH values and the significant increase in the acidity of N1-H (pK(a) approximately 5.6 as compared to 8.5 for N7 only bound platinum adducts), indicated by the pH dependence study of the H8 (1)H NMR resonance for the HT (head-to-tail) isomer of Rh(2)(OAc)(2)(5'-GMP)(2), are consistent with bidentate N7/O6 binding of the guanine. The H8 (1)H NMR resonance of the HH (head-to-head) Rh(2)(OAc)(2)(5'-GMP)(2) isomer, as well as the 5'-G and 3'-G H8 resonances of the Rh(2)(OAc)(2) [d(pGpG)] adduct exhibit pH-independent titration curves, attributable to the added effect of the 5'-phosphate group deprotonation at a pH value similar to that of the N1 site. The enhancement in the acidity of N1-H, with respect to N7 only bound metal adducts, afforded by the O6 binding of the bases to the rhodium centers, has been corroborated by monitoring the pH dependence of the purine C6 and C2 (13)C NMR resonances for Rh(2)(OAc)(2)(5'-GMP)(2) and Rh(2)(OAc)(2) [d(pGpG)]. The latter studies resulted in pK(a) values in good agreement with those derived from the pH-dependent (1)H NMR titrations of the H8 resonances. Comparison of the (13)C NMR resonances of C6 and C2 for the dirhodium adducts Rh(2)(OAc)(2)(5'-GMP)(2) and Rh(2)(OAc)(2) [d(pGpG)] with the corresponding resonances of the unbound ligands at pH 8.0, showed substantial downfield shifts of Deltadelta approximately 11.0 and 6.0 ppm, respectively. The HH arrangement of the bases in the Rh(2)(OAc)(2) [d(pGpG)] adduct is evidenced by intense H8/H8 ROE cross-peaks in the 2D ROESY NMR spectrum. The presence of the terminal 5'-phosphate group in d(pGpG) results in stabilization of one left-handed Rh(2)(OAc)(2) [d(pGpG)] HH1 L conformer, due to the steric effect of the 5'-group, favoring left canting in cisplatin-DNA adducts. Complete characterization of the Rh(2)(OAc)(2[d(pGpG)] adduct revealed notable structural features that resemble those of cis-[Pt(NH(3))(2) [d(pGpG)]]; the latter involve repuckering of the 5'-G sugar ring to C3'-endo (N-type) conformation, retention of C2'-endo (S-type) 3'-G sugar ring conformation, and anti orientation with respect to the glycosyl bonds. The superposition of the low energy Rh(2)(OAc)(2) [d(pGpG)] conformers, generated by simulated annealing calculations, with the crystal structure of cis-[Pt(NH(3))(2) [d(pGpG)]], reveals remarkable similarities between the adducts; not only are the bases almost completely destacked upon coordination to the metal in both cases, but they are favorably poised to accommodate the bidentate N7/O6 binding to the dirhodium unit. Unexpectedly, the two metal-metal bonded rhodium centers are capable of engaging in cis binding to GG intrastrand sites by establishing N7/O6 bridges that span the Rh-Rh bond.     

Near-infrared luminescent and magnetic cyano-bridged coordination polymers Nd(phen)n(DMF)m[M(CN)8] (M = Mo, W)

New cyano-bridged coordination polymers [Nd(phen)(2)(DMF)(2)(H(2)O)Mo(CN)(8)]·2H(2)O (1) and [Nd(phen)(DMF)(5)M(CN)(8)]·xH(2)O [M = Mo (2), W (3); phen = 1,10-phenanthroline] have one-dimensional structures with variable number of phenanthroline ligands. Compounds exhibit photoluminescence in the near-infrared region and ferromagnetic Nd(3+)-M(5+) interactions.     

Silver(I)-ethynide clusters constructed with phosphonate-functionized polyoxovanadates

Two neutral silver(I)-phenylethynide clusters incorporating the [((t)BuPO(3))(4)V(4)O(8)](4-) unit as an integral shell component, namely {(NO(3))(2)@Ag(16)(C≡CPh)(4)[((t)BuPO(3))(4)V(4)O(8)](2)(DMF)(6)(NO(3))(2)}·DMF·H(2)O and {[(O(2))V(2)O(6)](3)@Ag(43)(C≡CPh)(19)[((t)BuPO(3))(4)V(4)O(8)](3)(DMF)(6)}·5DMF·2H(2)O, have been isolated and characterized by X-ray crystallography. The central cavities of the Ag(16) and Ag(43) clusters are occupied by two NO(3)(-) and three [(O(2))V(2)O(6)](4-) template anions, respectively.     

Tetraarylpentaborates, [B(5)O(6)Ar(4)](-) (Ar = C(6)H(4)OMe-4, C(6)H(3)Me(2)-2,6): their formation from the reaction of arylboronic acids with an aryloxorhodium complex,structure, and chemical properties

The reactions of (4-methoxyphenyl)boronic acid (1a) and of (2,6-dimethylphenyl)boronic acid (1b) with (PMe(3))(3)Rh-(OC(6)H(4)Me-4) (2) in a 5:1 molar ratio result in the formation of cationic rhodium complexes with new tetraarylpentaborates [Rh(PMe(3))(4)](+)[B(5)O(6)Ar(4)](-) (3a, Ar = C(6)H(4)OMe-4; 3b, Ar = C(6)H(3)Me(2)-2,6). The characterization of 3a is as follows: orthorhombic space group P2(1)2(1)2(1), a = 14.7600(5) A, b = 17.1675(5) A, c = 19.8654(5) A; V = 5033.7(3) A(3); Z = 4. The characterization of 3b is as follows: orthorhombic space group Pnma, a = 23.704(6) A, b = 17.254(8) A, c = 13.304(2) A; V = 5441(2) A(3); Z = 4. An intermediate complex, [Rh(PMe(3))(4)](+)[Ph(3)B(3)O(3)(OC(6)H(4)Me-4)](-) (4), was isolated from the reaction of phenylboroxine, (PhBO)(3), with 2. The tetraarylpentaborates smoothly undergo hydrolysis to give [Rh(PMe(3))(4)](+)[B(5)O(6)(OH)(4)](-) (5).     

固相配位化学反应研究 XXXX: 硝普钠与锰(II)、钴(II)、镍(II)、铜(II)氯化物的固相反应

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