29162-73-0Relevant academic research and scientific papers
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.
Crystalline and permanently porous porphyrin-based metal tetraphosphonates
Rhauderwiek, Timo,Wolkersd?rfer, Konrad,?ien-?Degaard, Sigurd,Lillerud, Karl-Petter,Wark, Michael,Stock, Norbert
, p. 389 - 392 (2018)
The new porphyrin-based tetraphosphonic acid (Ni-H8TPPP) was employed in the synthesis of four isostructural MOFs of composition [M(Ni-H6TPPP)(H2O)], denoted CAU-29 (M = Mn, Co, Ni, Cd). Ni-CAU-29 was thoroughly characterized regarding its thermal and chemical stability as well as for proton conductivity.
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.
Efficient preparation of 5,10,15,20-tetrakis(4-bromophenyl)porphyrin. Microwave assisted v/s conventional synthetic method, X-ray and hirshfeld surface structural analysis
Matamala-Cea, Edison,Valenzuela-Godoy, Fabián,González, Déborah,Arancibia, Rodrigo,Dorcet, Vincent,Hamon, Jean-René,Novoa, Néstor
, (2020)
The symmetrical meso-tetrasubstituted porphyrin 5,10,15,20-tetrakis(4-bromophenyl)Porphyrin (1) has been synthesized in quite high yields, ranging from 55 – 78%, by conventional and microwave assisted techniques, and isolated as a microcrystalline compound. The products obtained in each case have been characterized by 1H NMR, Mass spectrometry, elemental analysis and Thin layer chromatography. The X-ray crystal structure of 1 is reported for the first time, and reveals a planar disposition of the center of the macrocycles with almost orthogonal 4-bromophenyl rings in the four meso-positions in the solid state. Hirshfeld surface (HS) analysis along with 2D fingerprint plots were employed to consider the intermolecular forces, including hydrogen bonds and π–π stacking interactions, and their quantification in the crystal lattice.
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.
Porphyrin-based porous polyimides: Synthesis, porous structure, carbon dioxide adsorption
Shi, Kaixiang,Song, Ningning,Zou, Yongcun,Zhu, Shiyang,Tan, Haiwei,Tian, Ye,Zhang, Bo,Yao, Hongyan,Guan, Shaowei
, p. 160 - 166 (2019)
A novel dianhydride 3,3’-bis(3,4-dicarboxyphenoxy)-4,4’-diphenylethynyl biphenyl dianhydride (BPEBPDA) and a new tetramine monomer 5,10,15,20- tetra[4-[(3-aminophenyl)ethynyl]phenyl]porphyrin (TAPEPP) were successfully synthesized. Porphyrin-based polyimides (PPBPIs) were synthesized from BPEBPDA and porphyrin-based building blocks (TAPP and TAPEPP) via polymerization reactions. The porphyrin-based porous polyimide networks (PPBPI-CRs) were obtained from PPBPIs through thermal crosslinking reactions. The PPBPI-CRs exhibited BET surface areas (682 m2 g?1 and 693 m2 g?1) and CO2 uptakes (2.0 mmol g?1 and 1.67 mmol g?1 at 273 K and 1 bar) as well as the separation factors of CO2/N2 (37.63, 28.97) and CO2/CH4 (7.51, 5.61). Meanwhile, PPBPI-CRs showed an enhanced CO2 isosteric enthalpies of adsorption (25.1 kJ mol?1 and 30.1 kJ mol?1) than other porous polymers.
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
Solar driven photocatalytic activity of porphyrin sensitized TiO2: Experimental and computational studies
Amuhaya, Edith K.,Derese, Solomon,Lanterna, Anabel E.,Mack, John,Nyokong, Tebello,Otieno, Sebastian,Scaiano, Juan C.
, (2021)
The absence of a secure long-term sustainable energy supply is recognized as a major world-wide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
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.
Manganese(III) mediated synthesis of A2B Mn(III) corroles: A new general and green synthetic approach and characterization
Yadav, Omprakash,Varshney, Atul,Kumar, Anil
, p. 168 - 171 (2017)
A new general and green synthetic protocol for the synthesis of manganese(III) metallocorroles has been developed from substituted aryl aldehydes and 5-(4-nitrophenyl)dipyrromethane using manganese salt as template. This is the first report in the synthesis of corroles: the formation of direct C–C bond through metal initiation. This method allows higher working concentrations than those previously reported. The new A2B manganese(III) metallocorroles were synthesized in good yield for different applications. The single crystal X-ray structure of 10-(3,4,5-fluorophenyl)-5,15-bis(4-nitrophenyl)manganese(III) corrole is also reported and shows that manganese atom is situating atop on macrocyclic plane.
