Synthesis of Covalently-Linked Linear Donor-Acceptor Copolymers Containing Porphyrins and Oligothiophenes

5,15-Di-bithienyl porphyrin (1) and its Cu(Ⅱ), Zn (Ⅱ) complexes (2 and 3)[1] were polymerized according to Scheme 1 by chemical oxidation using FeCl3 as oxidant for making organic conductor, and the linear porphyrin-thiophene copolymers were obtained. The structures of the copolymers were identified by elemental analysis and IR spectra. The conductivity of poly 5,15-di-bithienyl porphyrin (4) doped with FeCl3 was measured to reach over 10-6 S/cm, which was in the range of semiconductor and higher than that of other porphyrin-thiophene copolymers prepared by Shimidzu. The higher conductivity may be due to the better conjugation between the thienyl group and the porphyrin ring. The thienylporphyrins 7 and 8 could not be polymerized under the similar conditions, but could be polymerized by electrochemical oxidation (working electrode: gold-plate electrode; counter electrode: platinum; reference: standard calomel electrode SEC; solvent: 0.1 mol·dm-3 n-Bu4NClO4 in dry MeCN).     

电化学方法构筑直结型卟啉高分子

利用电化学方法成功地合成了不含其它连接基团的卟啉高分子,循环伏安图谱中发现该高分子在电极上的沉积为紧密型沉积,所得产物的紫外-可见吸收光谱表明相邻的卟啉环在该高分子链中均成平面直角结构,FT-IR图谱表明卟啉环之间是通过C-C键在meso位上相连,质谱图证明该高分子的链长可以达到13个卟啉环以上。     

Structure of Phenyl Derivatives of Octaethylporphyrin and Dissociation Kinetics of Their Mn3 +, Co2 +, and Cu2 + Complexes in Acetic Acid

Octaethyl-, 5-phenyloctaethyl-, 5,15-diphenyloctaethyl-, 5,10,15,20-tetraphenyloctaethyl, and dodecaphenylporphyrins were prepared, and their geometries were optimized by the method of molecular mechanics. The deformation of the porphyrin macroring grows as the number of phenyl groups is increased. The dissociation kinetics of the manganese, cobalt, and copper complexes of the porphyrins in solutions of sulfuric acid in acetic acid were studied. The kinetic parameters of the dissociation of metal porphyrins were analyzed in relation to the porphyrin structure and nature of the metal.     

Effect of terminal substituents on self‐assembly behavior of porphyrin molecules on Ag(110)

Effect of terminal substituents on self‐assembly behavior of porphyrin molecules has been studied with three derivatives modified with distinctly different substituents, 5,15‐(di‐3,5‐di‐tert‐butylphenyl) porphyrin, 5,15‐(dimesityl) porphyrin, and 5,15‐(di‐4‐ethynylphenyl) porphyrin. Scanning tunneling microscopy and density functional calculations reveal that 5,15‐(di‐3,5‐di‐tert‐butylphenyl) porphyrin, 5,15‐(dimesityl) porphyrin, and 5,15‐(di‐4‐ethynylphenyl) porphyrin spontaneously give different ordered structures on Ag(110) surface both at room temperature and after annealing. It is clear that the tert‐butylphenyl substituent could increase the intermolecular van der Waals interactions to form stable network structure under condition of thermal activation, whereas the mesityl substituent plays an essential role in the formation of rigid chain structure as a result of the CH–π interactions between the mesityl groups of molecule enantiomers. Moreover, the ethynylphenyl substituent could induce metal atoms to coordinate with ethynyl to form organometallic chains. Copyright © 2016 John Wiley & Sons, Ltd.     

聚类卟啉金属配合物*

为模拟天然卟啉所具有的特殊生理活性,结构与性能各异的多种金属卟啉被合成并应用于许多领域。实际上,天然金属卟啉是在特定天然高分子-蛋白质营造的空穴中才能发挥其独特的性质,因此,类卟啉金属配合物的高分子化逐渐受到关注,并在载氧、催化、导电等领域取得重要成果。基于结合方式不同,高分子类卟啉金属配合物可分为高分子担载类卟啉金属配合物与聚类卟啉金属配合物。其中,后者以稳定的类卟啉环作为高分子链,不但使高分子骨架稳定,而且活性中心与类卟啉金属配合物之间有效间隔,同时活性中心相对密集,使其表现出较高的稳定性与活性。线形与平面型聚金属卟啉与金属酞菁表现出良好的导电性与催化活性;手性Salen席夫碱易于聚合得到线形或网状聚Salen希夫碱金属配合物,其表现出较强的催化活性、高ee值和可循环性。异双核聚类卟啉金属配合物也表现出较强的催化活化分子氧性能。     

Kinetics of Oxidation of “Capped” Zinc Porphyrin Containing a 2,5-Dimethoxyphenylene “Cap” with Organic Peroxides in the Presence of Imidazole

Oxidation of the zinc complex of “capped” 5,15-[2,5-bis(2′-phenyleneoxymethyl)-1,4-dimethoxybenzene]-2,8,12,18-tetramethyl-3,7,13,17-tetrabutylporphyrin with organic peroxides in the presence of imidazole at 298 K results in complete breakdown of the complex. The nitrogen base exerts a significant effect on the rate of metal porphyrin oxidation. The kinetic parameters of the reaction were determined. The structures of the sterically strained metal porphyrin and intermediate products of its oxidation were optimized by PM3 calculations. A geometry analysis shows that the deformations of the macroring increase upon formation of the extra complex and its reaction with peroxides.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 847–853.Original Russian Text Copyright © 2005 by Zaitseva, Zdanovich, Koifman.     

Structure and coordination properties of sterically strained meso-alkyl-substituted Zn porphyrin

The formation of molecular complexes of zinc 5,15-dipentyl-2,3,7,8,12,13,17,18-octamethylporphin (ZnP) with nitrogen bases (L = 2-methylimidazole (2-Me-Im), imidazole (Im), pyridine (Py), 3,5-dimethylpyrazole (DMP), and dimethylformanmide (DMF)) was studied by spectrophotometric titration and quantum-chemical calculations. The stability constant was found to increase linearly with the basicity of the extra ligand and to be proportional to the shift of the fundamental absorption bands in the UV/Vis spectra. The structure of the compound formed as a result of the intermolecular interaction of the macrocyclic complex with a base was determined. The structures of zinc porphyrin and its extra complexes were optimized by the PM3 quantum chemical technique. The geometric and energetic characteristics of the compounds were obtained. A correlation between the calculated interaction energy of the central metal atom and the nitrogen atom of the extra ligand, on the one hand, and the stability of Zn porphyrin extra complexes, on the other hand, was established. The dependence of the zinc-extra ligand bond strength on the basicity of the additional molecular ligand was established. An effect of steric strain on the coordination properties of the metal porphyrin was noted.     

Porphyrin-acetylene-thiophene polymer wires

5,15-Bis[acetylene-4-(ethylenedioxy)thiophene]-10,20-bis(4-carboxyphenyl)porphyrin was synthesized by a Sonogashira coupling and polymerized to fibres; TEM and AFM images show uniform porphyrin wires with a length of several micrometers and a thickness of less than 4 nm.     

5,5,15,15-Tetraoxo-5,15-Dithiaporphyrin as a Highly Electron-Deficient Porphyrinic Ligand

Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield. The resultant 5,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently. Owing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwent facile axial ligation to form pentacoordinate and hexacoordinate high-spin (S=1) complexes in solution and solid, respectively. The binding constant of pyridine to the Ni^II center was significantly higher than those of conventional porphyrin Ni^II complexes. Temperature-dependent magnetic susceptibility measurements of the high-spin Ni^II complex revealed the presence of weak ferromagnetic interactions.     

Oxidation kinetics of Zn-5,15 bis(<Emphasis Type="Italic">ortho</Emphasis>-methoxyphenyl)-2,3,7,8,12,13,17,18-octamethylporphyrin with organic peroxides in <Emphasis Type="Italic">o</Emphasis>-xylene

With the purpose of further investigation of the effect of the steric strain of the porphyrin macroring in metal porphyrins on their redox properties, kinetics of oxidation of Zn-5,15 bis(ortho-methoxyphenyl)-2,3,7,8,12,13.17,18-octamethylporphyrin with organic peroxides in o-xylene at 295°C were studied spectrophotometrically to show that this process leads to complete destruction of the complex. Kinetic characteristics (k _ef, k _v) of the process were evaluated. The structure of the zinc porphyrin and its oxidation intermediates were obtained by quantum-chemical calculations. Steris strains in the metal prophyrin macroring were revealed and shown to enhance in the course of the reaction. An effect of the degree of deformational strain on the oxidation rate was noted.     

Directly linked porphyrin arrays

The Ag(I)-promoted oxidative meso-meso coupling reaction of 5,15-diaryl Zn(II)-porphyrin was serendipitously found in the course of our synthetic approaches towards photosynthetic reaction centers. Based on this reaction, a variety of directly linked and fused porphyrin arrays have been synthesized, including linear meso-meso-linked porphyrin arrays, windmill- and grid-shaped porphyrin arrays, meso-beta singly linked diporphyrins, beta-beta linked diporphyrins, meso-beta doubly linked (fused) diporphyrins and oligoporphyrins, meso-meso beta-beta doubly linked (fused) diporphyrins, and meso-meso beta-beta-beta-beta triply linked (fused) diporphyrins. The meso-meso coupling reaction of 5,15-diaryl Zn(II)-porphyrins is advantageous considering its high regioselectivity as well as its ease of extension to large porphyrin arrays as is demonstrated by the synthesis of a discrete meso-meso-linked 128-mer and poly(5,15-porphyrinylene). Finally, the oxidation of end-phenyl capped meso-meso-linked zinc porphyrins with DDQ-Sc(OTf)(3) gave pi-conjugated flat porphyrin tapes. To the best of our knowledge, the meso-meso linked 128-mer is the longest man-made discrete molecule, and the porphyrin tape 12-mer is the most extensively conjugated porphyrin array, as evinced by the lowest electronic band peak at 3500 cm(-1).     

Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1)

Double ring expansion from a 5,15‐diarylporphyrin to a 5,16‐diaryl‐10,11,21,22‐tetradehydro[20]porphyrin(2.1.2.1) occurred through a reaction sequence consisting of oxidation with PbO₂ to 5,15‐dioxoporphodimethene, a Corey–Fuchs reaction with tetrabromomethane in the presence of triphenylphosphine, and Fritsch–Buttenberg–Wiechell rearrangement triggered by tert‐butyllithium. The obtained tetradehydro[20]porphyrin(2.1.2.1) and its mono‐ and dihydrogenated congeners exhibited 20 π antiaromatic character, whereas overhydrogenated congeners bearing a saturated bridge were nonaromatic owing to disrupted π conjugation.     

Complexes of aryl-substituted porphyrins and naphthalenediimide (NDI): investigations by synchrotron X-ray diffraction and NMR spectroscopy

New donor-acceptor hybrids of Zn(II)-metallated 5,15-diaryl porphyrins have been designed and synthesised via the porphyrin interactions with an electron acceptor molecule, di-n-hexyl N-substituted 1,2,4,8-naphthalenetetracarboxylic diimide (NDI). Binding interactions within these supramolecular complexes were investigated in the solid state by synchrotron X-ray diffraction and probed in solution by (1)H NMR spectroscopy. The systematic modulation of the porphyrin π-density was achieved, for the first time as multiple methoxy and fluorine groups were introduced as substituents to the 5,15-diaryls of the porphyrin. For these, the variation of the porphyrin-NDI binding strengths determined by (1)H NMR titrations was shown, using the Swain's type dual parameter approach, to be closely linked with the peripheral substitution pattern of the diaryl porphyrins validated by crystallography. The new 1:1 donor-acceptor complexes formed display characteristic features of the aromatic-stacked systems, i.e. the parallel arrangement and short interplanar separation between the substituted porphyrin and NDI. Synthetic modification of electron-density on the porphyrin surface by introducing substituents at peripheral sites of functionalised porphyrins represent a general solution towards electronically tunable aromatic surfaces: an understanding of their solution and solid state behaviour will significantly improve the rational design of new functional donor-acceptor supramolecular materials with potential applications ranging from new energy materials to dye-sensitised solar cells, photovoltaics and future drug delivery devices.     

5,15-dialkyl-substituted tetrabenzoporphyrins and their zinc complexes. Synthesis and spectral properties

Reactions of phthalimide with capric and stearic acids gave 1-[1-(1-oxo-1H-isoindol-3-yl)nonylidene]-2,3-dihydro-1H-isoindol-3-one and 1-[1-oxo-1H-isoindol-3-yl)heptadecylidene]-2,3-dihydro-1H-isoindol-3-one, respectively. The latter were heated with zinc(II) acetate to obtain zinc complexes of 5,15-dioctyl-and 5,15-dihexadecyltetrabenzoporphyrins. The same complexes were synthesized by reaction of 1-(1-oxo-1H-isoindol-3-ylmethylidene)-2,3-dihydro-1H-isoindol-3-one with capric or stearic acid in the presence of zinc(II) oxide. The corresponding free porphyrin ligands were obtained by treatment of the metal complexes with sulfuric acid.     

低聚壳聚糖负载金属卟啉配合物的制备及生物活性研究

将低聚壳聚糖(COS)分别与不同卟啉金属(MTPPS4,M=Cu,Co,Zn)配合物结合,制备了水溶性低聚壳聚糖负载金属卟啉配合物(COS-MTPPS4),并采用红外光谱和紫外-可见光谱对其结构进行了表征。采用SRB细胞染色法,研究了壳聚糖负载金属卟啉(COS-MTPPS4)对人体肝癌细胞Bel-7402的抗肿瘤细胞活性。结果表明,金属离子配位到卟啉环中,使系列化合物对Bel-7402有较强的抑制生长活性,IC50值均小于100μg/mL,在10～20μg/mL范围内。水溶性低聚壳聚糖金属卟啉配合物作为抗肿瘤药物有很好应用前景。     

Deposition of thermally unstable molecules with the spray-jet technique on Au(111) surface

A porphyrin derivative (5,15-bis(4-ethynylphenyl)-10,20-bis(3,5-di-tert-butylphenyl)porphyrin: trans-BETBPP) possessing chemically reactive substituents was successfully deposited on an Au(111) surface with a new molecular beam deposition system with use of a spray-jet technique (Spray-jet-MBD) without denaturing the molecules. The deposited molecular overlayers were observed at 77 K under ultrahigh vacuum condition by scanning tunneling microscopy (STM). They form two different overlayer structures: a linear arrangement and a square lattice structure. In these overlayers, some molecules were accidentally moved by STM tip agitation, which indicates that the molecules were not polymerized during the deposition process.     

Directional synthesis of a dye-linked conducting homopolymer

We report a new synthesis of a 10,20-diphenyl-5,15-bis(4-cyanophenyl)porphyrin (1) and its reduction to give 10,20-diphenyl-5,15-bis(4-formylphenyl)porphyrin (2). When the conducting polymer poly(2',5'-dioctyl-4,4' '-terphenylenecyanovinylene) was prepared in the presence of 2, we obtained a three-domain structure, compound 3, consisting of two homopolymer blocks (J domains) with the porphyrin dye molecule (P domain) in the middle. The JPJ assembly was subjected to photophysical studies where we showed that the J domain could serve as a light-harvesting antenna for the P domain.     

ms-四咪唑基卟啉络合金属离子的能力及其金属络合物的催化性能

本文考察了两种ms-四咪唑基卟啉〔H₂T(2-I)P和H₂T(4或5-I)P〕对锌离子的络合能力,并与ms-四苯基卟啉〔H₂TPP〕进行了比较。用ms-四咪唑基金属卟啉〔MT(2-I)P和MT(4或5-I)P〕作为催化剂,以分子氧为氧源,考察了对氢醌、异丙硫醇和抗环血酸三种底物氧化反应的催化活性。在后一底物的氧化反应中对CoT(2-I)P,CoT(4或5-I)P和CoTPP进行了对比。此外,还用EHMO程序计算了卟吩、ms-四咪唑基卟啉、ms-四苯基卟啉及其锌络合物的净电荷分布和能量,对反应结果作了比较满意的解释。     

Synthesis and investigation of 2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-bis(2-thienyl)-21H,23H-porphin and its complexes with manganese (III) acetate and chloride

2,8,12,18-Tetrabutyl-3,7,13,17-tetramethyl-5,15-bis(2-thienyl)-21H,23H-porphin and its complexes with manganese(III) with additional acetate and chloride acido ligands were synthesized. Basing on the UV, IR, and NMR spectra and the kinetic properties of the proton transfer and the dissociation of free and coordinated porphyrin respectively it was established that in the change of porphyrin basicity at thienyl substitution the effect of the sulfur atom vacant d-orbitals involved in the conjugation was predominant. The stability of thienyl-substitued complexes of manganese(III) rises when the axial Cl^? is replaced by acetate ion.     

Investigations of rotamers in diaxial Sn(IV)porphyrin phenolates—towards a molecular timepiece

An approach to the formation of molecular timepieces is outlined based on differentiating between rotamers in diaxial Sn(IV) porphyrin phenolates. Two models are explored in detail. The first explores how the rates of rotation of the diaxial ligands is discriminated based on steric hindrance of the two porphyrin macrocycle faces at low temperature. The second model explores a ‘stopwatch’ function based on the ligation of Ag(I) ions to a 5,15-dipyridylporphyrinato tin(IV) complex bearing 3-hydroxypyridine ligands. The complexation inhibits rotation of the axial ligand, a result, which can be reversed by precipitation of Ag(I) using tetraethylammonium bromide. X-ray crystallography has also been used to characterize two Ag(I) 5,15-dipyridylporphyrinato tin(IV)complexes. The two isoforms differ in their supramolecular organization. One structure is formed through a cofacial stack linking each porphyrin by Ag(I) coordination. The other displays a sheet-like coordination polymer structure.