超临界二氧化碳中卟啉与钴(II)、镍(II)、锌(II)配合物反应动力学

用紫外-可见光谱研究了钴(II)、镍(II)、锌(II)的1,1,1,5,5,5-六氟-2,4-戊二酮-二水配合物[M(hfac)2(H2O)2,M=Co、Ni、Zn]与5,10,15,20-四(五氟苯基)卟啉[H2tpfpp]在超临界二氧化碳中反应生成金属卟啉[M(tpfpp)]的反应动力学.在金属配合物大大过量时,反应对卟啉为一级.其表观一级速率常数随钴(II)、镍(II)配合物的浓度增加先增加、而后趋于稳定,而表观一级速率常数随锌(II)配合物的浓度增加线形增加.根据实验事实,讨论了反应的机理,得到了相应的热力学和动力学参数.     

超临界二氧化碳中卟啉与钴(II)、镍(II)、锌(II)配合物反应动力学

用紫外-可见光谱研究了钴(II)、镍(II)、锌(II)的1, 1, 1, 5, 5, 5-六氟-2, 4-戊二酮-二水配合物[M(hfac)2(H₂O)₂, M=Co、Ni、Zn]与5, 10, 15, 20-四(五氟苯基)卟啉[H2tpfpp]在超临界二氧化碳中反应生成金属卟啉[M(tpfpp)]的反应动力学. 在金属配合物大大过量时, 反应对卟啉为一级. 其表观一级速率常数随钴(II)、镍(II)配合物的浓度增加先增加、而后趋于稳定, 而表观一级速率常数随锌(II)配合物的浓度增加线形增加. 根据实验事实, 讨论了反应的机理, 得到了相应的热力学和动力学参数.     

一个新型钌(II)配合物对F－的双重光谱识别

采用紫外-可见光谱和荧光光谱滴定方法研究了钌(II)配合物[Ru(bpy)(H2iip)2](ClO4)2 [bpy＝2,2’-联吡啶, H2iip＝2-吲哚基-咪唑并[4,5-f][1,10]-邻菲罗啉]在DMSO溶液中对卤素离子的识别性质. 结果表明该配合物能比色和荧光双重光谱高选择性识别F－.     

低相变温度锌卟啉液晶的合成与表征

卟啉液晶作为一种功能型盘状液晶,已经受到了科学家们的高度重视^[1]。自1980年Goodby^[2]首次合成出简单的卟啉液晶以来;各国学者对卟啉液晶的合成做了相应的研究工作,但其液晶相变温度偏高^[3,4],相区宽度偏窄^[3]。本文首次合成出相变温度较低,相区宽,含有8,10,12和14碳的酰氧基的四种卟啉液晶5、10、15、20－四（对－酰氧基）苯基卟啉液晶5、10、15、20－四（对－酰氧基）苯基卟啉锌（Ⅱ）配合物[分别简称为TOPPZn,TDPPZn,TLPPZn,TMPPZn]。研究4种配合物的液晶行为,其液晶相相变温度最低始于－36．4℃,相区宽达175℃,是一种具有应用前景的卟啉液晶。     

对苯二甲酸根桥联的双核铬(Ⅱ)配合物的合成与磁性

以对苯二甲酸根（TPHA）为桥联配体,分别端接4,4'－二甲基－2,2'－联化吡啶（Me2bpy),2,9－二甲基－1,10－邻菲啉（Me2phen)和5－毛－1,氯－1,10－邻菲啉（Cl-phen),合成了3种新的双核铬（III）配合物[Cr2-(TPHA)(Me2bpy)4]（NO3）4,[Cr2(TPHA)(Me2phen)4](2)[Cr2(TPHA)(Me2phen)4](3).经元素分析,摩尔电导和磁性测定以及红外光谱和电子光谱等手段,这些配合物具有TPHA桥联双核铬（III）结构,其中,每个铬（III）离子处于畸变八面体配位环境,测定了配合物（1）的变曙磁化率（4－300K）,其数值用最小二乘法和从自旋Hamiltonian算符（H＝－2JS1S2)导出的磁议程 拟合,求得交换积分为－2．98cm^1,结果表明双核配合物中金属离子间存在弱的反铁磁自旋交换作用。     

手性锌卟啉的圆二色光谱研究

用圆二色光谱（CD）研究了三种新型手性卟啉锌[α,β,α,β－四－[邻（叔丁氧羰L－丙氨酸）氨基苯基]卟啉锌α,β,α,β,－ZnT(o-BocAla)APP1、α,β,α,β-四－[邻（叔丁氧羰L－脯氨酸）氨基苯基]卟啉锌α,β,α,β－ZnT(o-BocPro)APP2和α,β,α,β－甲－[邻（苯甲酰L－谷酰胺）氨基苯基]卟啉锌α,β,α,β－ZnT(o-BenzoylGln)APP3]在CH2Cl2 中的光谱行为,并研究了1作为主体识别手性客体分子氨基酸甲酯前后的光谱,提出了光谱形成机理。     

5-(4-丙氨酸丁氧苯基)-10,15,20-三苯基卟啉及其配合物的合成和性质

本文首次合成了一种 新型的单取代的丙氨酸四苯基卟啉，５－（４－丙氨酸丁氧苯基）－１０，１５，２０－三苯基卟啉（Ｈ２Ｌ），及其Ｃｏ（ｄ２）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）配合物用元素分析，电子光谱，红外光谱，荧光光谱和激光拉曼光谱进行表征。     

同、异双核卟啉-Salen型金属配合物的合成及非线性光学性质

设计合成了两种新型卟啉-Salen 型配体5-（3-氨基-4-（3,5-二叔丁基水杨醛基）-氨基苯基）-10,15,20-三苯基卟啉（1）和5-（N,N’-二（3,5-二叔丁基水杨醛基）-3,4-二氨基苯基）-10,15,20-三苯基卟啉（2）及其同、异双核金属配合物和单金属核配合物. 采用氢核磁共振（1H NHR）谱、电喷雾质谱（ESI-MS）、傅里叶变换红外（FTIR）光谱和紫外-可见（UV-Vis）光谱等手段对各目标化合物进行了表征. 用Z扫描技术研究了配体及其金属配合物的三阶非线性光学性质. 实验结果表明：配体1和配体2具有相似的光学特征,均具有反饱和吸收的特性和自散焦效应;当不同的金属离子嵌入配体形成单、双核金属配合物后,分子的极性发生改变,他们的光学特性均受到影响.     

钴(Ⅱ)配合物与卟啉在超临界二氧化碳中的反应动力学研究

用紫外-可见光谱研究了1,1,1,5,5,5-六氟-2,4-戊二酮-钴(Ⅱ)二水[Co(hfac)2(H2O)2]与5,10,15,20-四(五氟苯基)卟啉(H2tpfpp)在超临界二氧化碳中反应生成钴卟啉[Co(tpfpp)]的反应动力学.在钴(II)配合物大大过量时,此反应对卟啉为一级,且其表观一级速率常数随钴(Ⅱ)配合物的浓度增加先增加、而后趋于稳定.根据实验事实,讨论了此反应的机理,得到了相应的热力学和动力学参数.     

金属卟啉及其与NO表面吸附物的FT—IR／PAS研究

光声光谱(Photoacoustic Spectroscopy,PAS)是研究凝聚态和表面吸附物振动光谱的1种新方法。近几年来PAS发展很快,它与FT-IR技术结合,已成为1种新的固体样品和表面分析的有力工具。本文应用FT-IR/PAS方法研究了金属卟啉配合物及其与NO的表面吸附物。卟啉及其金属配合物具有平面大π体系共轭环的结构特点,在光     

四(对-十八酰氧基)苯基卟啉及其过渡金属配合物的合成及红外光声光谱研究

合成了5,10,15,20-四(对-十八酰氧基)苯基卟啉及其Mn(Ⅲ),Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)和Zn(Ⅱ)配合物,用元素分析和紫外-可见光谱等方法进行了表征.研究了这7种卟啉化合物在3600～190cm^-1范围内的傅里叶变换红外光声光谱,对主要谱带进行了经验归属.结果表明,3318.0及968.4cm^-1处的吸收谱带分别是四(对-十八酰氧基)苯基卟啉N-H键的伸缩振动和面内弯曲振动,生成配合物后这些谱带消失.243cm^-1附近的吸收谱带是M-N键伸缩振动和卟啉环变形振动的复合振动,321cm^-1附近的吸收谱带是M-Cl键的伸缩振动,金属敏感带出现在1350,1018,995,802,740,632和232cm^-1附近.     

四(对-十二酰氧基苯基)卟啉配合物的红外光声光谱

四(对-十二酰氧基苯基)卟啉配合物的红外光声光谱     

四-(对-十二酰氧基)苯基卟啉过渡金属配合物的合成及其液晶行为研究

合成了5,10,15,20-四-(对-十二酰氧基)苯基卟啉(简称TLPPH₂)及其Mn(Ⅲ),Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)和Zn(Ⅱ)配合物,通过元素分析、紫外可见光谱、红外光声光谱、核磁共振氢谱和摩尔电导等分析方法表征了它们的组成和结构.用DSC和偏光显微镜研究了配体及其锌配合物的液晶行为.结果表明,锌配合物的液晶相变温度始于-50.67℃,相区宽度达143℃.     

FTIR－PAS技术在卟啉类化合物中的应用（Ⅲ）──乙酰丙酮－meso－四－（对－氯代）苯基卟啉稀土配合物的红外光声光谱

研究乙酰丙酮－ｍｅｓｏ－四－（对－氯代）苯基卟啉及其Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｌｕ配合物在３６００～２２０ｃｍ－１范围内的傅立叶变换红外光声光谱，对其主要谱带进行经验归属．实验结果表明，四－（对－氯代）苯基卟啉与稀土乙酰丙酮配合物中的金属离子配位，削弱乙酰丙酮环上的Ｍ－Ｏ键伸缩振动，使该谱带向低波数方向移动．金属敏感带出现在～１５５８、～１４７４、～１４２７、～１２１９、～７９８、～７３３、～２５０ｃｍ－１．     

Energy funneling of IR photons captured by dendritic antennae and acceptor mode specificity: anti-stokes resonance raman studies on iron(III) porphyrin complexes with a poly(aryl ether) dendrimer framework

A series of poly(aryl ether) dendrimer chloroiron(III) porphyrin complexes (LnTPP)Fe(III)Cl (number of aryl layers [n]=3 to 5) were synthesized, and their Boltzmann temperatures under IR irradiation were evaluated from ratios of Stokes to anti-Stokes intensities of resonance Raman bands. While the Boltzmann temperature of neat solvent was unaltered by IR irradiation (LnTPP)Fe(III)Cl (n=3 to 5), all showed a temperature rise that was larger than that of the solvent and greater as the dendrimer framework was larger. Among vibrational modes of the metalloporphyrin core, the temperature rise of an axial Fe-Cl stretching mode at 355 cm-1 was larger than that for a porphyrin in-plane mode at 390 cm-1. Although most of the IR energy is captured by the phenyl nu8 mode at 1597 cm-1 of the dendrimer framework, an anti-Stokes Raman band of the phenyl nu8 mode was not detected, suggesting the extremely fast vibrational relaxation of the phenyl mode. From these observations, it is proposed that the energy of IR photons captured by the aryl dendrimer framework is transferred to the axial Fe-Cl bond of the iron porphyrin core and then relaxed to the porphyrin macrocycle.     

四(对-辛酰氧基)苯基卟啉配合物的红外光声光谱

测试并研究了四(对-辛酰氧基)苯基卟啉及其Mn(Ⅲ)、Fe(Ⅲ)、co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)配合物在3600～190cm^-1范围内的傅立叶变换红外光声光谱,对主要谱带进行了经验归属.结果表明:3318.0和968.0cm^-1处的吸收谱带分别是四(对-辛酰氧基)苯基卟啉N-H键的伸缩振动和面内弯曲振动,生成配合物后这些谱带消失.～243cm^-1处的吸收谱带是M-N键伸缩振动和卟啉环变形振动的复合振动,～320cm^-1处的吸收谱带是M-Cl键的伸缩振动,金属敏感带出现在1504,1350,1022,995,796和235cm^-1处.     

稀土元素与L-酪氨酸和甘氨酸三元固态配合物的合成及表征

目前稀土与氨基酸三元固态配合物的研究着重于少数稀土-氨基酸-非氨基酸类型.本文报道了10种稀土与L-酪氨酸(Tyr,HO——CH_2(NH_2)CHCOOH)和甘氨酸(Gly,NH_2CH_2COOH)三元固态配合物的合成及FTIR光谱、质谱表征.     

Synthesis of Vinylene-Co,N-Linked Multi(porphyrin)s by the Addition of Free-Base Porphyrins to a C(2)H(2) Complex of Cobalt(III) Porphyrin and Their Oxidative Rearrangement to Vinylene-N,N'-Linked Multi(porphyrin)s

The nucleophilic addition reaction of a pyrrole nitrogen of free-base porphyrins to a pi-complexed acetylene ligand in a cationic Co(III) porphyrin intermediate afforded good yields of vinylene-Co,N'-linked bis(porphyrin)s, (Por)Co(III)-CH=CH-(N-Por)H(2). N-substituted porphyrin free bases are N-vinylated regioselectively at the pyrrole adjacent to the original N-substituted pyrrole in this reaction. Tris- and tetrakis(porphyrin)s have been prepared by reacting a vinylene-N,N'-linked bis(meso-tetraarylporphyrin) with (OEP)Co(III)(H(2)O)(2)ClO(4) (OEP: octaethylporphyrin dianion) and acetylene. The tetrakis(porphyrin) proved to be a 1:1 mixture of C(i)()- and C(2)-symmetric regioisomers. These organometallic Co(III) complexes underwent facile oxidative migration of the Co-bound vinyl group to a porphyrin pyrrole nitrogen when treated with Fe(III) salts or HClO(4) to provide moderate to good yields of Co(II) vinylene-N,N'-linked multi(porphyrin) complexes. (Vinylene-N,N')bis(porphyrin) free bases with combinations of different porphyrins have been obtained by this procedure. The homobinuclear (2Co(II), 2Cu(II), and 2Zn(II)) and heterobinuclear (Co(II)Cu(II) and Co(II)Zn(II)) complexes have been prepared and characterized spectroscopically. The single-crystal X-ray analysis of (CH=CH-N,N')[(OEP)Co(II)Cl][(TPP)Zn(II)Cl] (TPP: meso-tetraphenylporphyrin dianion) showed a face-to-face structure with an average inter-ring separation of 4.39 ? (triclinic P&onemacr;; Z = 2; a = 14.806(4), b = 18.703(10), c = 13.796(3) ?, alpha = 97.69(3), beta = 99.57(2), gamma = 96.74(3) degrees ).     

RESONANCE RAMAN SPECTRA OF THE II-CATION RADICALS OF COPPER, COBALT, AND NICKEL METHYLOCTAETHYLCHLORINS: VIBRATIONAL CHARACTERISTICS OF CHLOROPHYLL MODELS

Abstract— By using excitation at 363.8 nm, resonance Raman (RR) spectra were obtained for Cu(II), Co(II), and Ni(II) complexes of methyloctaethylchlorin (MeOEC) and their ir-cation radicals. Additionally, the Raman spectra of the Cu(II) derivatives of (rarcs-octaethylchlorin (r-OEC) were included for comparison. The alkyl-substituted CuMeOEC exhibits a Raman spectrum that is nearly identical to that of the simpler (-CuOEC in both the neutral and oxidized states. Unlike the latter species, the cation radical of CuMeOEC is immune to oxidative dehydrogenation to porphyrin, and this has facilitated vibrational characterization of the ring-oxidized species. This study aims to compare the vibrational characteristics in the 1450 to 1700 cm^-t region of the metallochlorin ir-cation radicals to those of the corresponding oxidized metalloporphyrins. We focus on two modes in the1500–1520 cm^-1 and1620–1650 cm^-1 region that are analogous to the v₃ and v₁₀ vibrations, respectively, in the metalloporphyrin analogs. These vibrational modes are clearly defined in all species and exhibit a strong core-size dependency in the porphyrin complexes. The core-size study as well as the frequency changes upon oxidation support the conclusion that the v₃-like vibration in the chlorin species features substantial C_bC_b in addition to C_aC_m stretching character. The v,₀-like mode of the chlorin macrocycle, on the other hand, displays characteristics that closely resembles that of the porphyrin analog; consequently, these vibrations are of predominantly C_aC_m stretching character in both cases.     

Through Bridge Spin Coupling in Homo- and Heterobimetallic Porphyrin Dimers upon Stepwise Oxidations: A Spectroscopic and Theoretical Investigation

We have described copper(II)-iron(III) and copper(II)-manganese(III) heterobimetallic porphyrin dimers and compared them with the corresponding homobimetallic analogs. UV-visible spectra are very distinct in the heterometallic species while electrochemical studies demonstrate that these species, as compared to the homobimetallic analog, are much easier to oxidize. Combined Mössbauer, EPR, NMR, magnetic and UV-visible spectroscopic studies show that upon 2e-oxidation of the heterobimetallic complexes only ring-centered oxidation occurs. The energy differences between HOMO and LUMO are linearly dependent with the low-energy NIR band obtained for the 2e-oxidized complexes. Also, strong electronic communication between two porphyrin rings through the bridge facilitates coupling between various unpaired spins present while the coupling model depends on the nature of metal ions used. While unpaired spins of Fe(III) and the porphyrin π-cation radical are strongly antiferromagnetically coupled, such coupling is rather weak between Mn(III) and a porphyrin π-cation radical. Moreover, the coupling between two π-cation radicals are much stronger in the 2e-oxidized complexes of dimanganese(III) and copper(II)-manganese(III) porphyrin dimers as compared to their diiron(III) and copper(II)-iron(III) analogs. Furthermore, coupling between the unpaired spins of a π-cation radical and copper(II) is much stronger in the 2e-oxidized complex of copper(II)-iron(III) porphyrin dimer as compared to its copper(II)-manganese(III) analog. The Mulliken spin density distributions in 2e-oxidized homo- and heterobimetallic complexes show symmetric and asymmetric spread between the two macrocycles, respectively. In both the 2e-oxidized heterobimetallic complexes, the Cu(II) porphyrin center acts as a charge donor while Fe(III)/Mn(III) porphyrin center act as a charge acceptor. The experimental observations are also strongly supported by DFT calculations.