2，9，16，23-四羧基酞菁钴(Ⅱ)与硫醇、硫酚配位反应的热力学研究

我们研究了2,9,16,23-四羧基酞菁钴(Ⅱ)与硫醇(2-巯基乙醇)、硫酚(苯硫酚)轴向配位反应的热力学性质,发现了配位过程中中心离子钴由二价变为一价的现象。用紫外-可见分光光度法和Miller-Dorough数据处理方法,确定了体系的配位数和平衡常数;利用温度系数法求得了体系的Δ_rH^?_m, Δ_rS^?_m。探讨了温度对反     

含两个酰胺基团的卟啉二聚体分子间氢键引起的发光光谱红移

通过5-（4-甲酸基苯基）-10,15,20-三（4-十二烷氧基苯基）卟啉（HAcTPP）与乙二胺,丙二胺和丁二胺反应,制备了一类含2个酰胺基团的卟啉二聚体C₂（AmTPP）₂、C₃（AmTPP）₂和C₄（AmTPP）₂以及相应的配合物Pt2C₂（AmTPP）₂、Pt2C₃（AmTPP）₂和Pt2C₄（AmTPP）₂。采用¹H NMR、¹³C NMR、质谱、元素分析、循环伏安、紫外-可见吸收光谱和荧光发射光谱等对二聚体的化学结构、热稳定性、电化学和光物理性质进行了表征。实验发现,二聚体和相应的铂配合物的光致发光（PL）光谱性质与溶液的浓度有关,在10^-7 mol·L^-1 THF稀溶液中,二聚体与单羧基卟啉的PL光谱基本一致。当浓度增加到10^-3 mol·L^-1 THF溶液时,二聚体的光致发光光谱最大值从657 nm红移到675 nm,比单羧基卟啉红移了18 nm。当与金属铂配位后,这种发射光谱随浓度增加而变化的特性更加明显。二聚体配合物在10^-7 mol·L^-1 THF稀溶液中PL光谱就产生了红移现象,最大发射峰λ_max为673 nm,比单羧基卟啉红移16 nm。在高浓度10^-4 mol·L^-1 THF溶液和升华薄膜中的PL最大发射峰进一步红移到727 nm的近红外区。进一步,为了证实二聚体配合物分子间的π-π和Pt-Pt相互作用,我们以配合物Pt2C₃（AmTPP）₂为例,对二聚体配合物固体在常温和低温77 K的PL光谱进行了测试,发现固体配合物表现出与温度相关的PL性质。当温度降到77 K时,配合物的最大发射峰从658 nm红移到674 nm,红移了16 nm。实验表明,卟啉二聚体和相应的配合物的红移现象与二聚体的分子结构直接相关,卟啉二聚体中的两个酰胺基团能够产生较强的分子间氢键,导致二聚体分子之间产生一定程度的π-π和Pt-Pt相互作用,使得二聚体PL光谱产生红移。     

系列Ln(Ⅲ)配位聚合物的合成、结构及光物理性能(Ln(Ⅲ)=Yb、Ho、Er)

采用水热方法合成了3个Ln(Ⅲ)配位聚合物：[Ln(NH₂-C₆H₄-COO)₂DMF(HCOO)(H₂O)]_n(Ln=Yb 1,Ho 2,Er 3);通过X-单晶衍射、红外光谱(IR)、紫外吸收光谱(UV-Vis-NIR)、发射光谱(紫外可见荧光光谱和近红外发射光谱)等方法对化合物进行了表征。结果表明,化合物1、     

meso-四(对烷氧基苯基)卟啉锌配合物的合成、表征及热力学性质

合成得到系列meso-四(对烷氧基苯基)卟啉及其锌配合物的晶体，其结构经 ¹H NMR，UV-Vis和元素分析确证。研究了配合物与吲哚客体的轴向配位热力学性质。结果表明:主体与客体的配位数均为1;不同主体的平衡常数与电子效应和空间效应有关。研究了温度对平衡常数的影响，发现平衡常数随温度升高而降低。根据平衡常数计算了配合过程的热力学参数Δ_rH_m^?，Δ_rS_m^?和Δ_rG_m^?，结果表明反应为放热、熵减过程。     

N-皮考林酰肼及其双核钯配合物的晶体结构和荧光性质

合成了配体N-皮考林酰肼(简写为Hphz)及其双核钯配合物[Pd₂(phz)₂Cl₂]. X射线衍射实验结果表明, 配体和配合物晶体均属于单斜晶系, 空间群分别为C 2/c和P 2₁/c, 分子式分别为C₆H₇N₃O和C₁₂H₁₂Cl₂N₆O₂Pd₂. 晶体学参数, Hphz, a＝1.9245(2) nm, b＝0.38927(2) nm, c＝1.8073(2) nm, b＝107.255(2)°, V＝1.2931(2) nm³, Z＝8, D_c＝1.409 Mg/m³, F(000)＝576, μ(Mo Kα)＝0.102 mm^－1, R＝0.0541, wR＝0.1762; [Pd₂(phz)₂Cl₂], a＝1.48274(9) nm, b＝1.44797(9) nm, c＝0.73951(5) nm, b＝92.719(3)°, V＝1.5860(2) nm³, Z＝4, D_c＝2.329 Mg/m³, F(000)＝1072, μ(Mo Kα)＝2.62 mm^－1, R＝0.0262, wR＝0.0555. 在配合物[Pd₂(phz)₂Cl₂]分子内, 两个钯(II)原子, 均呈畸变的N₃Cl平面正方形配位构型, 晶体内通过分子间氢键N—H…Cl 作用形成一维链状结构, 分子间吡啶环存在相互作用. 量子化学从头算方法计算结果表明, 分子内及分子间的金属钯之间也存在相互作用. 红外光谱表明, 配体在形成配合物后, ν(C＝O)和ν(C＝N)红移, ν(C—N)蓝移, 荧光光谱表明, 配合物金属对配体n-π*激发(310 nm)引起的发射峰有较大的影响.     

叔丁基亚胺四氯合钽(V)阴离子配合物[IPrH]+[tBuN=TaCl4(py)]-的合成与表征

[^tBuN=TaCl₃(py)₂]和氮杂环卡宾(IPr =1,3-bis(2,6-diisoproylphenyl)imidazol-2-ylidene)的反应得到预料之外的叔丁基亚胺四氯合钽(V)离子配合物[IPrH]⁺[^tBuN=TaCl₄(py)]- (1)。利用核磁共振波谱,红外吸收光谱,荧光光谱,元素分析和X-Ray单晶衍射对配合物1的结构进行了表征。X-射线单晶衍射分析表明,Ta(V)中心与4四个氯和2个分别来自亚胺和吡啶配体的氮原子以八面体构型配位。     

一维链状3-碘苯甲酸铽配合物的合成、晶体结构和性质表征

溶液法合成了配合物{[Tb(3-IBA)₃(H₂O)₂]·0.5(4,4′-bipy)}_n(3-IBA=3-碘苯甲酸根;4,4′-bipy=4,4′-联吡啶),并通过X-射线衍射单晶结构分析、红外光谱、紫外光谱、荧光光谱以及热重分析对配合物进行了结构和性质表征。配合物晶体属三斜晶系,P1空间群。该配合物具有一维链状结构。Tb³⁺离子与8个O原子配位,其中6个O原子来自5个3-碘苯甲酸根,2个O原子来自水分子。相邻Tb³⁺离子通过2个双齿桥联的3-碘苯甲酸根联结成一维链状结构。未配位的4,4′-联吡啶分子与配位水分子之间形成氢键,并将相邻的一维链联结起来形成二维网状结构。沿a轴的分子堆积形成一维孔道,是由于相邻一维链的苯环之间部分重叠而形成的。在紫外光照射下,配合物发出很强的绿色荧光。配合物的荧光光谱中,4个峰位于490、544、583和619 nm,分别对应于Tb³⁺离子的⁵D₄→⁷F₆、⁵D₄→⁷F₅、⁵D₄→⁷F₄和⁵D₄→⁷F₃跃迁。     

荧光法研究偏钒酸钠与牛血清白蛋白的相互作用

本文用荧光光谱和紫外可见吸收光谱研究了在模拟人体生理条件下，偏钒酸钠与牛血清白蛋白(BSA)结合反应的特征，研究了紫外灯(253.7 nm)照射对偏钒酸钠与BSA结合的影响。紫外吸收光谱显示，加入偏钒酸钠后，牛血清白蛋白的紫外吸收降低，表明偏钒酸钠与BSA形成了缔合物。荧光猝灭光谱显示偏钒酸钠对牛血清白蛋白有较强的荧光猝灭作用，荧光猝灭机理符合静态机制。缔合物的稳定常数分别为：K_s=0.357×10⁴(25 ℃)，K_{s相似文献}   

配合物[Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA)的水热合成、晶体结构及量子化学研究

以醋酸铜、间三氟甲基苯甲酸(m-TFBA)和邻菲咯啉(phen)为原料在甲醇水介质中通过水热反应,合成了一个新的单核 铜?髤配合物[Cu(m-TFBA)(phen)(H₂O)₂]·(m-TFBA),用元素分析、红外光谱和热重分析对配合物进行了表征。X-射线单晶衍射表明,配合物属三斜晶系,空间群P1,晶胞参数：a=1.001 61(10) nm,b=1.150 69(12) nm,c=1.286 49(12) nm,α=82.217(2)°,β=84.767(2)°,γ=66.371(2)°,V=1.344 8(2) nm³,Z=2,D_c=1.625 g·cm^-3,R₁[I>2σ(I)]=0.042 1,wR₂[I>2σ(I)]=0.095 8。铜(Ⅱ)分别与来自邻菲咯啉的2个氮原子、间三氟甲基苯甲酸的1个氧原子和2个水分子中的2个氧原子配位,形成变形的四方锥结构。配合物通过强的O-H…O氢键作用形成了二聚体结构,该二聚体又通过分子间弱的C-H…O氢键作用形成了一维链状结构。配合物中配位的间三氟甲基苯甲酸上的三氟甲基基团具有无序结构。对配合物中[Cu(m-TFBA)(phen)(H₂O)₂]⁺进行了量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。     

配合物[Co(qina)2(H2O)2]•2DMSO的晶体结构及其与DNA作用研究

合成了配合物[Co(qina)₂(H₂O)₂]•2DMSO单晶(qina为喹哪啶酸). 配合物属于单斜晶系, P2(1)/n空间群, 其分子结构为规则的八面体构型, qina以氮原子和羧酸根氧原子与Co^2＋离子配位, 两个水分子为轴向配位. 配合物之间富有配位水分子分别与DMSO的氧原子、qina中未与Co(II)配位的氧之间氢键作用. 配合物与鱼精DNA作用的紫外光谱和荧光光谱表明, 两者之间有一定的相互作用, 并可能以局部插入方式为主.     

通过轴向配位反应实现4-乙烯基吡啶聚合物的卟啉功能化

通过轴向配位反应,将四苯基卟啉锌(ZnTPP)键合在4-乙烯基吡啶(4VP)与苯乙烯(St)共聚物P(4VP-co-St)的侧链,制得了卟啉功能化的大分子ZnTPP-P(4VP-co-St).通过FTIR与1H-NMR对其化学结构进行了表征,重点研究了时间、温度对轴配过程的影响,以及大分子轴配化合物ZnTPP-P(4VP-co-St)的谱学性能,对其光物理行为进行了较为深入的分析.研究结果表明,以共聚物P(4VP-co-St)的吡啶侧基为配体,通过轴向配位反应可顺利地制备卟啉功能化的大分子ZnTPP-P(4VP-co-St),且温度越低,键合量越大.该大分子具有类似于ZnTPP的特征电子吸收光谱与荧光发射光谱,同时也显示出轴向配位的特征.与小分子ZnTPP相比,ZnTPP-P(4VP-co-St)的吸收光谱和发射光谱都发生了明显的红移.大分子轴配化合物ZnTPP-P(4VP-co-St)的光物理行为也呈现出一定程度的高分子效应,随着大分子链中ZnTPP键合量的增大,相近的ZnTPP侧链单元之间会发生能量转移,使荧光发射强度有所减弱.     

Enhanced electron transfer ability <Emphasis Type="Italic">via</Emphasis> coordination in block copolymer/porphyrin/fullerene micelle

Inspired by structures of antenna-reaction centers in photosynthesis, the complex micelle was prepared from zinc tetra-phenyl porphyrin (ZnTPP), fullerene derivative (PyC₆₀) and poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL). The core-shell structure made the hydrophobic donor-acceptor system work in aqueous. In micellar core, coordination interaction occurred between ZnTPP and PyC₆₀ molecules which ensured the enhanced energy migration from the donor to the acceptor. The enhanced interaction between porphyrin and fullerene was confirmed by absorption, steady-state fluorescence and transient fluorescence. The generation of singlet oxygen and superoxide radical was detected by iodide method and reduction of nitro blue tetrazolium, respectively, which confirmed that electron transfer reaction in the complex micellar core occurred. Moreover, the complex micelle exhibited effective electron transfer performance in photodebromination of 2,3-dibromo-3-phenylpropionic acid. The complex micellar structure endowed the donor-acceptor system with improved stability under irradiation. This strategy could be helpful for designing new electron transfer platform and artificial photosynthetic system.     

金属卟啉/异烟酸/二氧化钛复合光催化剂制备及其光催化性能研究

合成了四苯基卟啉(H2TPP)及铜卟啉(CuTPP)和锌卟啉(ZnTPP),获得了配合物[Zn(TPP)(DMF)]的晶体。制备了金属卟啉、异烟酸共修饰的二氧化钛复合光催化剂:金属卟啉/异烟酸/二氧化钛,红外光谱和X-射线衍射(XRD)分析结果表明金属卟啉和异烟酸负载于TiO2表面,未改变TiO2的晶型。在光催化降解水中污染物4-硝基苯酚(4-NP)时显示了好的催化效果。     

ENERGY TRANSFER FROM SODIUM N-ALKYL CARBAZOLE SULFONATE TO ZINC TETRAPHENYLPORPHYRIN IN MICELLAR SOLUTIONS

Abstract— In order to study energy transfer to zinc tetraphenylporphyrin (ZnTPP) in micellar solution, a series of surface active agents of sodium N-alkyl carbazole sulfonate, were synthesized. The energy transfer efficiency from the carbazole group near the surface to ZnTPP located in the core of sodium lauryl sulfate (NaLS) micelles was found to be 30%, as observed through the fluorescence of ZnTPP. The critical micelle concentrations (CMC) of the sodium N-alkyl carbazole sulfonate surfactants, determined by scattering, were 2 times 10_-4 M, 3 times 10_-5M and 3 times 10_-6 M, respectively, for alkyl: octyl, dodecyl and hexadecyl. The sensitivity of the CMC of NaLS to the presence of foreign surfactants and solubilizates was also investigated.     

Enhanced Electron Transfer Ability via Coordination in Block Copolymer/Porphyrin/Fullerene Micelle

Inspired by structures of antenna-reaction centers in photosynthesis,the complex micelle was prepared from zinc tetra-phenyl porphyrin (ZnTPP),fullerene derivative (PyC60) and poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-bPCL).The core-shell structure made the hydrophobic donor-acceptor system work in aqueous.In micellar core,coordination interaction occurred between ZnTPP and PyC60 molecules which ensured the enhanced energy migration from the donor to the acceptor.The enhanced interaction between porphyrin and fullerene was confirmed by absorption,steady-state fluorescence and transient fluorescence.The generation of singlet oxygen and superoxide radical was detected by iodide method and reduction of nitro blue tetrazolium,respectively,which confirmed that electron transfer reaction in the complex micellar core occurred.Moreover,the complex micelle exhibited effective electron transfer performance in photodebromination of 2,3-dibromo-3-phenylpropionic acid.The complex micellar structure endowed the donor-acceptor system with improved stability under irradiation.This strategy could be helpful for designing new electron transfer platform and artificial photosynthetic system.     

Diiron propanedithiolate complex bearing the pyridyl-functionalized phosphine ligand axially coordinated to a photosensitizer zinc tetraphenylporphyrin

Treatment of the starting material (μ-PDT)Fe₂(CO)₆ (PDT = SCH₂CH₂CH₂S) with 4-diphenylphosphinoaminopyridine (PyNHPPh₂) in the presence of the decarbonylating agent Me₃NO·2H₂O afforded (μ-PDT)Fe₂(CO)₅(PyNHPPh₂) (1) in 56% yield. Further treatment of 1 with Zinc tetraphenylporphyrin (ZnTPP) yielded the target light-driven model compound (μ-PDT)Fe₂(CO)₅(PyNHPPh₂)(ZnTPP) (2) in 94% yield. The new complexes 1 and 2 were characterized by elemental analysis, NMR, IR, and X-ray crystallography. The molecular structure of 2 revealed its precursor 1 and a photosensitizer ZnTPP joined together through axial coordination. Furthermore, the fluorescence emission spectra and electrochemistry were also investigated.     

Highly Soluble Porphyrin (TPP)-Perylene Diimide (PDI) Dyad and Triad:Synthesis and Spectroscopic Studies

Novel porphyrin‐perylene diimide dyad (TPP‐PDI) and porphyrin‐perylene diimide‐porphyrin triad (TPP‐PDI‐TPP) were synthesized and characterized. Their structure and properties were studied by UV, FL, ¹H NMR, MS, elemental analysis, etc. The variation of fluorescence feature and UV spectra of TPP‐PDI‐TPP triad were investigated at different concentration of CF₃COOH in THF. The incorporation of CF₃COOH leads to the closure of the efficient charge transfer decay. After protonation of porphyrin units, the fluorescence intensity of TPP‐PDI‐TPP triad increased greatly. The fluorescence intensity of TPP‐PDI‐TPP triad restored after addition of triethylamine into the solution. Thus, TPP‐PDI‐TPP triad was a proton‐type fluorescence switch based on acid‐base control. Moreover, different from porphyrin‐perylene type molecular switches reported before, this TPP‐PDI‐TPP triad has wonderful solubility in organic solvents.     

强磁场对四苯基卟啉及其Co(Ⅱ)/Zn(Ⅱ)配合物的影响

为研究强磁场对卟啉类化合物的影响,以四苯基卟啉(TPP)为研究对象,比较分析了无外加磁场和强磁场条件下TPP的结晶,及Co~(2+)、Zn~(2+)与TPP的配位反应。采用X射线粉末衍射测试不同磁场强度下获得的TPP晶体,紫外分光光度计快速测定了不同磁场强度下配合物产率,并分析了配位反应的动力学。TPP的结晶度随磁场强度的增强而提高,晶体尺寸随磁场强度的增加而增大;随磁场的增强,四苯基钴卟啉(CoTPP)和四苯基锌卟啉(ZnTPP)的产率下降,但两者的反应动力学不受磁场影响,其反应速率随磁场强度提高而下降。由研究结果可知,强磁场有利于四苯基卟啉的结晶取向,四苯基卟啉在溶液中垂直于磁场取向是配位反应速率降低的主要原因,随磁场强度的增加,四苯基卟啉的取向程度提高。     

Photochemical study of the zinc cis-3-(4-imidazolylphenyl)-1-(pyridin-2-yl)[60]fullereno[1,2-c]pyrrolidine-meso-tetraphenylporphyrinate dyad

Axial coordination of fullerenopyrrolidine bearing the donor imidazolyl group, cis-3-(4-imidazolylphenyl)-1-(pyridin-2-yl)[60]fullereno[1,2-c]pyrrolidine (C₆₀∼Im), with zinc meso-tetraphenylporphyrinate (ZnTPP) in an o-dichlorobenzene solution affords a non-covalently bonded donor-acceptor dyad ZnTPP-C₆₀∼Im. The photochemical behavior of the ZnTPP-C₆₀∼Im complex was studied by fluorescence (excitation at λ = 420 nm) and laser kinetic spectroscopy (excitation at λ = 532 nm, 12 ns). The formation constant of the 1: 1 porphyrin-fullerenopyrrolidine complex determined from quenching of ZnTPP fluorescence assuming static intracomplex quenching is 1.6·104 L mol⁻¹. Absorption spectra of the excited states in the system consisting of ZnTPP and Im∼C₆₀ (ZnTPP/C₆₀∼Im) were measured in solution from 380 to 1000 nm. The quenching constant of the triplet-excited ZnTPP with fullerenopyrrolidine C₆₀∼Im was determined. The results obtained indicate the formation of the triplet exciplex {PL}^* ⇌ {P^δ+…L^δ−} in the ZnTPP/C₆₀∼Im system upon laser photolysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1541–1547, September, 2006.     

Photoinduced Charge Separation in Zinc–Porphyrin/Tungsten–Alkylidyne Dyads: Generation of Reactive Porphyrin and Metallo Radical States

The luminescent tungsten–alkylidyne metalloligand [WCl(≡C‐4,4′‐C₆H₄CC‐py)(dppe)₂] ( 1 ; dppe=1,2‐bis(diphenylphosphino)ethane) and the zinc–tetraarylporphyrins ZnTPP and ZnTP_ClP (TPP=tetraphenylporphyrin, TP_ClP=tetra(p‐chlorophenyl)porphyrin) self‐assemble in fluorobenzene solution to form the dyads ZnTPP( 1 ) and ZnTP_ClP( 1 ), in which the metalloligand is axially coordinated to the porphyrin. Excitation of the porphyrin‐centered S₁ excited states of these dyads initiates intramolecular energy‐transfer (ZnPor→ 1 ) and electron‐transfer ( 1 →ZnPor) processes, which together efficiently quench the S₁ state (～90 %). Transient‐absorption spectroscopy and an associated kinetic analysis reveal that the net product of the energy‐transfer process is the ³[dπ*] state of coordinated 1 , which is formed by S₁→¹[dπ*] singlet–singlet (Förster) energy transfer followed by ¹[dπ*]→³[dπ*] intersystem crossing. The data also demonstrate that coordinated 1 reductively quenches the porphyrin S₁ state to produce the [ZnPor^?][ 1⁺ ] charge‐separated state. This is a rare example of the reductive quenching of zinc porphyrin chromophores. The presence in the [ZnPor^?][ 1⁺ ] charge‐separated states of powerfully reducing zinc–porphyrin radical anions, which are capable of sensitizing a wide range of reductive electrocatalysts, and the 1⁺ ion, which can initiate the oxidation of H₂, produces an integrated photochemical system with the thermodynamic capability of driving photoredox processes that result in the transfer of renewable reducing equivalents instead of the consumption of conventional sacrificial donors.