29162-73-0Relevant articles and documents
Palladium-catalyzed cross-coupling reaction of a chiral ferrocenyl zinc reagent with aromatic bromides: Application to the design of chiral octupoles for second harmonic generation
Mamane, Victor,Ledoux-Rak, Isabelle,Deveau, Sandrine,Zyss, Joseph,Riant, Olivier
, p. 455 - 467 (2003)
Palladium catalyzed cross coupling reaction of a chiral ferrocenylzinc reagent with aryl bromides allowed the introduction of a planary chiral ferrocenyl subunit on an aryl fragment. Using this method, new C3 symmetric chiral architecture bearing organometallic donor-acceptor fragments were assembled starting from a common tris aldehyde precursor. The non- linear optical properties were measured using the Harmonic Light Scattering method and the potentiality for the new chromophores to behave as octupoles is also discussed.
Guest-tuned proton conductivity of a porphyrinylphosphonate-based hydrogen-bonded organic framework
Wang, Yijie,Yin, Jianbo,Liu, Di,Gao, Chengqi,Kang, Zixi,Wang, Rongming,Sun, Daofeng,Jiang, Jianzhuang
, p. 2683 - 2688 (2021)
Hydrogen-bonded organic frameworks (HOFs), similar to their MOF analogues, exhibit great potential in proton conduction applications. Herein, a porous HOF namely [(NiH4TPPP)(Me2NH2)4(DMF)(H2O)4] (UPC-H5) was synthesized from phosphonate-based porphyrinato nickel (NiH8TPPP), and its proton conductivity is regulated through a two-step guest change. Firstly, immersing UPC-H5 in CH2Cl2to exchange lattice solvent molecules for 24 h followed by heating under vacuum afforded the lattice solvent molecule-free HOF [(NiH4TPPP)(Me2NH2)4] (UPC-H5a) with the pristine framework still retained. Secondly, exposing UPC-H5a to vapors of 25% aqueous ammonia for 24 h at room temperature gave a new derivative UPC-H5a@NH3·H2O with the molecular formula [(NiH4TPPP)(Me2NH2)2(NH4)2(H2O)4] according to elemental and thermal analyses. At 30 °C and 95% R.H., the proton conductivity of UPC-H5, UPC-H5a, and UPC-H5a@NH3·H2O amounts to 5.59 × 10?4, 7.00 × 10?3, and 1.47 × 10?2S cm?1, respectively, which increases to 1.85 × 10?3, 3.42 × 10?2, and 1.59 × 10?1S cm?1at 80 °C and 99% R.H., clearly showing the effect of guest regulation on the proton conductivity of the HOF-based materials. In addition, this result is also helpful towards understanding the important role of guests in the formation of their proton conduction pathways.
A Porous Cobalt Tetraphosphonate Metal–Organic Framework: Accurate Structure and Guest Molecule Location Determined by Continuous-Rotation Electron Diffraction
Wang, Bin,Rhauderwiek, Timo,Inge, A. Ken,Xu, Hongyi,Yang, Taimin,Huang, Zhehao,Stock, Norbert,Zou, Xiaodong
, p. 17429 - 17433 (2018)
Single-crystal electron diffraction has shown to be powerful for structure determination of nano- and submicron-sized crystals that are too small to be studied by single-crystal X-ray diffraction. However, it has been very challenging to obtain high quality electron diffraction data from beam sensitive crystals such as metal–organic frameworks (MOFs). It is even more difficult to locate guest species in the pores of MOF crystals. Here, we present synthesis of a novel porous cobalt MOF with 1D channels, [Co2(Ni-H4TPPP)]?2 DABCO?6 H2O, (denoted Co-CAU-36; DABCO=1,4-diazabicyclo[2.2.2]octane), and its structure determination using continuous rotation electron diffraction (cRED) data. By combining a fast hybrid electron detector with low sample temperature (96 K), high resolution (0.83–1.00 ?) cRED data could be obtained from eight Co-CAU-36 crystals. Independent structure determinations were conducted using each of the eight cRED datasets. We show that all atoms in the MOF framework could be located. More importantly, we demonstrate for the first time that organic molecules in the pores, which were previously difficult to find, could be located using the cRED data. A comparison of eight independent structure determinations using different datasets shows that structural models differ only on average by 0.03(2) ? for the framework atoms and 0.10(6) and 0.16(12) ? for DABCO and water molecules, respectively.
Exploring supramolecular self-assembly of tetraarylporphyrins by halogen bonding: Crystal engineering with diversely functionalized six-coordinate tin(L)2-porphyrin tectons
Titi, Hatem M.,Patra, Ranjan,Goldberg, Israel
, p. 14941 - 14949 (2013)
This study targets the construction of porphyrin assemblies directed by halogen bonds, by utilizing a series of purposely synthesized Sn(axial ligand)2-(5,10,15,20-tetraarylporphyrin) [Sn(L)2-TArP] complexes as building units. The porphyrin moiety and the axial ligands in these compounds contain different combinations of complimentary molecular recognition functions. The former bears p-iodophenyl, p-bromophenyl, 4'-pyridyl, or 3'-pyridyl substituents at the meso positions of the porphyrin ring. The latter comprises either a carboxylate or hydroxy anchor for attachment to the porphyrin-inserted tin ion and a pyridyl-, benzotriazole-, or halophenyl-type aromatic residue as the potential binding site. The various complexes were structurally analyzed by single-crystal X-ray diffraction, accompanied by computational modeling evaluations. Halogen-bonding interactions between the lateral aryl substituents of one unit of the porphyrin complex and the axial ligands of neighboring moieties was successfully expressed in several of the resulting samples. Their occurrence is affected by structural (for example, specific geometry of the six-coordinate complexes) and electronic effects (for example, charge densities and electrostatic potentials). The shortest intermolecular I×××N halogen-bonding distance of 2.991A was observed between iodophenyl (porphyrin) and benzotriazole (axial ligand) moieties. Manifestation of halogen bonds in these relatively bulky compounds without further activation of the halophenyl donor groups by electron-withdrawing substituents is particularly remarkable. Porphyrins in tandem: Porphyrin-based network materials can been supramolecularly organized into one-dimensional and two-dimensional structures by means of cooperative directional halogen bonding (see figure). Copyright
Cobalt/nitrogen co-doped porous carbon nanosheets as highly efficient catalysts for the oxygen reduction reaction in both basic and acidic media
Hou, Zongsheng,Yang, Chongqing,Zhang, Wenbei,Lu, Chenbao,Zhang, Fan,Zhuang, Xiaodong
, p. 82341 - 82347 (2016)
Porous carbon materials have been widely developed as catalysts for the oxygen reduction reaction (ORR) under basic conditions but very few under acidic conditions. In this work, two-dimensional (2D) cobalt/nitrogen co-doped porous carbon nanosheets were prepared as catalysts for the ORR under both basic and acidic conditions by using a cobalt porphyrin based 2D conjugated microporous polymer as a precursor. Remarkably, the as-prepared porous carbon nanosheets exhibited excellent electrochemical catalytic performance for the ORR, with a low half-wave potential (E1/2) at -0.146 V in 0.1 M KOH and 0.54 V in 0.5 M H2SO4 (versus Ag/AgCl) as well as a dominant four-electron transfer mechanism (n = 3.8 at -0.28 V in 0.1 M KOH; n = 3.8 at 0.55 V in 0.5 M H2SO4). The high catalytic ORR performance can be attributed to the high activity of CoNx active sites as well as the high specific surface area that derived from the cobalt porphyrin blocks among the conjugated microporous polymer nanosheets. It's believed that this method opens up new avenues for metal/heteroatom co-doped porous carbon materials with promising performance for energy storage and conversion.
Palladium catalyzed carbonylation of Br-substituted porphyrins
Vinogradov, Sergei A.,Wilson, David F.
, p. 8935 - 8938 (1998)
The Pd-catalyzed carbonylation of Br-substituted porphyrins is reported. Several new alkoxycarbonylporphyrins are synthesized in good yields. The reaction is found particularly useful for derivatization of the tetrabenzoporphyrin system.
A novel metalloporphyrin-based conjugated microporous polymer for capture and conversion of CO2
Sheng, Xingfeng,Guo, Hongchen,Qin, Yusheng,Wang, Xianhong,Wang, Fosong
, p. 31664 - 31669 (2015)
A novel conjugated microporous polymer was solvothermally synthesized using an aluminum porphyrin as a main building block, which had a high Brunauer-Emmett-Teller specific surface area up to 839 m2 g-1 and a pore volume of 2.14 cm3 g-1. The polymer displayed excellent capacity to capture carbon dioxide (4.3 wt%) at 273 K and 1 bar, and good catalytic activity for cyclic carbonate synthesis with TOF up to 364 h-1.
Facile synthesis of poly(BODIPY)s via solid state polymerization and application in temperature sensor
He, Guohang,Li, Ying,Lu, Qingyi,Xia, Jiangbin,Xu, Feng,Zhang, Dongkui
, (2022/01/14)
Several 3,5-dibromo substituted BODIPY (4,4′-Difluoro-4-bora-3a,4a-diaza-s-indacene) derivatives were rationally designed and investigated as potential candidates to perform solid state polymerization (SSP). Compared with the traditional systems of thiophene and diacetylene families, which were successfully applied in SSP, SSP has been expanded to the BODIPY system in this article. In addition, crystallographic data of BODIPY derivative was derived to analyze the reasonable path of SSP, which could further explore the mechanism of SSP. Furthermore, the relationship between fluorescence intensity of BODIPY after SSP and temperature was established, which could apply this material in temperature fluorescence sensor with outstanding relative sensitivity (Sr) of 0.898% K?1. Our work has been proved to pave the way to explore more conjugated systems by using SSP method and enrich SSP database systematically.
Asymmetrically meso-substituted porphyrin derivative containing the triazole group: Synthesis, characterization and photo-physicochemical properties
Harmandar, Kevser,Tun?, Gülenay,Kü?ük, Tu?ba,Gürek, Ay?e Gül,Atilla, Devrim
, p. 78 - 83 (2021/08/25)
In this study, a novel asymmetrically meso-substituted AB3 porphyrins derivative including one triazole group to enhance the anticancer activity of the molecule and three bromophenyl groups to improve photochemical properties has been synthesized and characterized. Our objectives were to generate a system with triazole and bromophenyl groups that enhance the singlet oxygen generation and exhibits an anti-cancer effect. Therefore, photophysical and photochemical properties of this asymmetric porphyrin derivative (AB3) and the symmetric derivative (B4) were investigated in THF. The substituent effect on fluorescence quantum yield and singlet oxygen generation was evaluated for efficiency in photodynamic therapy (PDT) as a photosensitizer. The molecules exhibited no aggregation tendency, solubility in common organic solvents and high singlet oxygen quantum yield in THF therefore these favorable properties make them good candidates as a photosensitizer for PDT.
Catalytic activity of bis p-nitro A2B (oxo)Mn(V) corroles towards oxygen transfer reaction to sulphides
Kumar, Anil,Varshney, Atul,Yadav, Sunil
, (2020/10/02)
The 5 A2B Mn(III) corroles have been synthesized, fully characterized and used for oxygen atom transfer (OAT) from isolated (oxo)manganese(V)corrole to sulfide. Oxidation of Mn(III) were carried out using ozone, a clean oxidant, which resulted
