Self-assembled supramolecular architecture with alternating porphyrin and phthalocyanine, bonded by hydrogen bonding and π–π stacking

Tong, Shan-Ling; Zhang, Jing; Yan, Yan; Hu, Sheng; Yu, Jian; Yu, Lin

doi:10.1016/j.solidstatesciences.2011.08.026

Cited by 9 publications

(3 citation statements)

References 18 publications

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“…The hexacoordinate Mn center lies perfectly in the plane of the porphyrin and is axially ligated by two MeTHF molecules. The length of the bond between the manganese and the axially-ligated MeTHF molecule, Mn−O ax, , of 2.272(3) Å was within the range reported for other hexacoordinate Mn(III) porphyrins with two O-based ligands ( Table S2 ) [ 42 , 43 , 44 , 45 , 46 , 47 ]. Moreover, the longer Mn−O ax distances, as compared to Mn−N por (i.e., average of 2.008 Å) were in accord with the presence of a high-spin tetragonally elongated Mn(III) center.…”

Section: Resultssupporting

confidence: 74%

Dioxygen Reactivity of Copper(I)/Manganese(II)-Porphyrin Assemblies: Mechanistic Studies and Cooperative Activation of O2

Khan

Hematian

2022

Molecules

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The oxidation of transition metals such as manganese and copper by dioxygen (O2) is of great interest to chemists and biochemists for fundamental and practical reasons. In this report, the O2 reactivities of 1:1 and 1:2 mixtures of [(TPP)MnII] (1; TPP: Tetraphenylporphyrin) and [(tmpa)CuI(MeCN)]+ (2; TMPA: Tris(2-pyridylmethyl)amine) in 2-methyltetrahydrofuran (MeTHF) are described. Variable-temperature (−110 °C to room temperature) absorption spectroscopic measurements support that, at low temperature, oxygenation of the (TPP)Mn/Cu mixtures leads to rapid formation of a cupric superoxo intermediate, [(tmpa)CuII(O2•–)]+ (3), independent of the presence of the manganese porphyrin complex (1). Complex 3 subsequently reacts with 1 to form a heterobinuclear μ-peroxo species, [(tmpa)CuII–(O22–)–MnIII(TPP)]+ (4; λmax = 443 nm), which thermally converts to a μ-oxo complex, [(tmpa)CuII–O–MnIII(TPP)]+ (5; λmax = 434 and 466 nm), confirmed by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy. In the 1:2 (TPP)Mn/Cu mixture, 4 is subsequently attacked by a second equivalent of 3, giving a bis-μ-peroxo species, i.e., [(tmpa)CuII−(O22−)−MnIV(TPP)−(O22−)−CuII(tmpa)]2+ (7; λmax = 420 nm and δpyrrolic = 44.90 ppm). The final decomposition product of the (TPP)Mn/Cu/O2 chemistry in MeTHF is [(TPP)MnIII(MeTHF)2]+ (6), whose X-ray structure is also presented and compared to literature analogs.

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Section: Resultssupporting

confidence: 74%

Dioxygen Reactivity of Copper(I)/Manganese(II)-Porphyrin Assemblies: Mechanistic Studies and Cooperative Activation of O2

Khan

Hematian

2022

Molecules

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“…Non-covalent interactions, including π-π stacking, electrostatic interaction, hydrogen bonding, and halogen bonding, have been extensively utilized in materials science for controlling self-assembled structures. [21][22][23] We postulated that electrostatic and hydrogen bonding between PVDF and additives play an important role in determining the PVDF chain configuration due to highly dipolar C-F bonds. For the selection of additive, it was carefully considered not only the capability of forming the non-covalent interactions with PVDF but also the complete and easy removal of additive.…”

Section: Resultsmentioning

confidence: 99%

High β‐phase Poly(vinylidene fluoride) Using a Thermally Decomposable Molecular Splint

Choi

Lee

et al. 2022

Adv Elect Materials

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of large-area thin-film, micro-patterning, low-temperature process, and flexibility. [7,8] Ferroelectric polymers such as polyvinylidene fluoride (PVDF) have been investigated as alternatives to their inorganic counterparts. It is known that C-F dipoles in PVDF align parallel to the external electric field, and remanent polarization remains after removing the field, which leads to piezoelectricity and pyroelectricity in PVDF. Depending on preparation methods, PVDF exhibited several different crystalline phases, including α, β, γ, δ, and ε. While β-phase PVDF, whose backbone chain configuration is all trans, presents the highest ferroelectricity, non-ferroelectric α-phase is dominantly observed when PVDF is prepared by thermal crystallization method since trans-gauche alternating structure is thermodynamically most stable.There have been a lot of efforts in preparing β-rich PVDF, including stretching, copolymerization with trifluoroethylene (TrFE), or adding organic/inorganic additives. [9][10][11] Stretching αor γ-phase PVDF leads to β-phase PVDF, but the enhancement of β-phase (<85%) is practically limited by relatively low drawing ratio. [12] PVDF-TrFE has several advantages exhibiting high β-phase (≈90%) and eligibility of thin-film process. However, PVDF-TrFE copolymers easily lose ferroelectricity at elevated temperatures because they An additive, 1,4-butadiene sulfone (BDS), which generates H 2 SO 3 by in situ thermal retro-Diels-Alder decompositions, is used for preparing high β-phase polyvinylidene fluoride (PVDF) films. Because of preferential multiple noncovalent interactions of H 2 SO 3 with all-trans configuration of PVDF, β-phase PVDF is spontaneously induced without mechanical drawing and/or extensive thermal annealing process. PVDF films cast from PVDF/BDS/water solutions exhibit high β-phase content (f β = 95%) when the BDS concentration is only c BDS = 1.0 wt%, which is confirmed by polarized optical microscopy (POM), SEM, Fourier transform infrared spectroscopy (FT-IR), differential scan calorimetry (DSC), and 2D grazing incidence wide-angle X-ray scattering (GIWAXS). Because of the high β-phase content, PVDF films prepared by using BDS exhibit excellent ferroelectric and piezoelectric properties (E c = 50 MV/m, P r = 5 µC/cm 2 , and d 33 = ≈-25 pm/V). Furthermore, a triboelectric nanogenerator (TENG) developed with high β-phase PVDF film exhibits enhanced performance as 2.5 times higher than neat PVDF film in output charge density, allowing reliable operation of conventional electronic devices.

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“…40 Besides the interaction types mentioned above, there were also other non-covalent interactions involved in the porphyrinpolymer assembly, such as p-p interaction. 41 Nevertheless, these non-covalent interactions never work alone. They may act synergistically in any combination to achieve the desired effect and to meet the application needs.…”

Section: Straightforward Self-assembly Of Porphyrins and Polymersmentioning

confidence: 99%

Cooperative self-assembly of porphyrins with polymers possessing bioactive functions

Zhao

et al. 2016

Chem. Commun.

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Natural porphyrin derivatives possess many interesting functions in biological systems. They are integrated into proteins that are essential for biological activities. Many efforts have been dedicated to mimic the microenvironment and augment the function of porphyrin/protein scaffolds. To achieve such goals, self-assembly has become one of the popular methods to construct porphyrin/protein-mimicking materials owing to its various choices of building blocks and a simple preparation process over chemical modification. Desirable characteristics of building blocks for protein mimicking include high molecular weight, predictable conformations in solution, and appropriate functional residuals. With these aims in mind, polymers are ideal candidates due to their multiple-level hierarchies derived from their chemical and spatial structures. In this review, design strategies for the cooperative self-assembly of porphyrins with polymers and the main efforts towards the implementation of porphyrin/polymer assembly for biomimetic composites with bioactive functions will be addressed.

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Self-assembled supramolecular architecture with alternating porphyrin and phthalocyanine, bonded by hydrogen bonding and π–π stacking

Cited by 9 publications

References 18 publications

Dioxygen Reactivity of Copper(I)/Manganese(II)-Porphyrin Assemblies: Mechanistic Studies and Cooperative Activation of O2

Dioxygen Reactivity of Copper(I)/Manganese(II)-Porphyrin Assemblies: Mechanistic Studies and Cooperative Activation of O2

High β‐phase Poly(vinylidene fluoride) Using a Thermally Decomposable Molecular Splint

Cooperative self-assembly of porphyrins with polymers possessing bioactive functions

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