| 1. |
- Ma, C. B., et al.
(författare)
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Great framework variation of polymers in the manganese(II) maleate/alpha,alpha' - Diimine system : Syntheses, structures, and magneto-structural correlation
- 2003
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :15, s. 2872-2879
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Tidskriftsartikel (refereegranskat)abstract
- Three novel manganese(II) coordination polymers, [Mn (maleate)(phen)](n) (1; phen = 1,10-phenanthroline), [Mn-(maleate)(phen)](n).nH(2)O (2), and [Mn(maleate)(bpy)](n) (3; bpy = 2,2'-bipyridine), have been synthesized by treatment of Mn2+ with maleic acid with participation of chelate diimine ligands, and have been identified by single-crystal, X-ray diffraction to have either one-dimensional (1D) zigzag chain structures (1 and 2) or a two-dimensional (2D) sinuous layer structure (3). Each maleate dianion coordinates to three Mn centers, in different bridging modes (syn-anti in 1 and 2, syn-syn and anti-anti in 3). These compounds represent an interesting example of structural topology variation from 1D to 2D mediated by chemically similar auxiliary chelate ligands. Variable-temperature magnetic susceptibility measurements show weak anti-ferromagnetic exchange interactions between the adjacent Mn-II ions, with J = -0.06 cm(-1) (2) and J = -1.3 cm(-1), zJ' = -0.27 cm(-1) (3). The differences in the magnitudes of these coupling interactions agree well with the nature of the carb oxylate-bridging coordination of maleate.
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| 2. |
- Gao, W. M., et al.
(författare)
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Synthesis, structures and electrochemical properties of amino-derivatives of diiron azadithiolates as active site models of Fe-only hydrogenase
- 2006
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Ingår i: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693 .- 1873-3255. ; 359:4, s. 1071-1080
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Tidskriftsartikel (refereegranskat)abstract
- The preparation and characterization of two novel amino-incorporated sulfur-bridged dinuclear iron (I) complexes of the type [NR(mu-SCH2)2]Fe-2(CO)(6), one being amino protected [N(CH2CH2NHTs)(mu-SCH2)(2)]Fe-2(CO)(6) (8) and the other [(mu-SCH2)(2)Fe-2(-CO)(6)NCH2CH2N (mu-SCH2)(2)]Fe-2(CO)(6) (9) are described. These two complexes are readily prepared in a S(N)2 manner between double lithium anion and bis(chloromethyl) amine derivatives. The structures of 8 and 9 were characterized by IR, H-1, C-13 NMR, MS and HRMS spectra and further determined by X-ray analyses. Protonation of complex 8 gave the mono N-protonated product, while for 9 the protonation occurred in both of the N atoms. The redox properties were evaluated by cyclic voltammograms. It was shown that these two complexes can catalyze electrochemical reduction of proton to molecular hydrogen.
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| 3. |
- Gao, Y. L., et al.
(författare)
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Crystal structure and electrochemical behavior of copper complex with 6-hydroxymethyl-substituted tris(2-pyridylmethyl) amine, CuCl(C19H20N4O) ClO4
- 2004
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Ingår i: Chinese journal of structural chemistry. - 0254-5861. ; 23:11, s. 1262-1265
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Tidskriftsartikel (refereegranskat)abstract
- A Cu(II) complex [CuCl(C19H20N40)]ClO4 1 containing hydroxymethyl substituted TPA (TPA = tris(2-pyridylmethyl)amine) was prepared. It crystallizes in monoclinic, space group P2(1)/c with a = 11.7628(2), b = 13.0083(3), c = 15.11280(10) Angstrom, beta = 108.724(2)degrees, V = 2190.09(7) Angstrom(3), M-r = 518.83, Z = 4, T = 293 (2) K, D-c = 1.574 g/cm(3), mu = 1.280 mm(-1), F(000) = 1060 and S = 1.085. The final R = 0.0543 and wR = 0.1433 for 2693 observed reflections with I >2sigma(I). The penta-coordinated copper (H) complex. assumes an approximate square pyramidal geometry. Cyclic voltammetry measurement of the complex showed a quasi-reversible Cu-II/Cu-I redox couple with E-1/2 -0.467 v and DeltaE = 68 mv.
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| 4. |
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| 5. |
- Huang, D. G., et al.
(författare)
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Synthesis, structural characterizations and magnetic properties of a series of mono-, di- and polynuclear manganese pyridinecarboxylate compounds
- 2004
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :7, s. 1454-1464
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Tidskriftsartikel (refereegranskat)abstract
- Seven new manganese(II, III, IV) pyridinecarboxylate compounds (Et4N)[MnCl2(pic)(2)] (1, Hpic = picolinic acid) [MnCl(Pic)(2)(H2O)].H2O (2), [MnCl(pic)(H2O)2](n) (3), [Mn(Pic)(2)](n) (4), [MnCl(pic)](n) (5), [MnCl2(4-C5H4NHCOO)](n) (6) and [Mn2O2(pic)(4)] (7) were synthesized and structurally characterized. The picolinate ligand coordinates to the Mn ion forming a chelating five-membered ring which constructs diverse architectures by various bridging modes, such as mu-Cl, mu(1,1)(-) and mu(1,3)-carboxylate bridges (syn-syn and syn-anti modes). The interaction between the pyridyl rings is discussed, displaying a face-to-face pi-pi stacking for complex 6 and a T-shaped C-H...pi attraction for complex 4. Complex 3 has an infinite zigzag chain structure in which two neighboring Mn ions are linked by a carboxylate bridge in a syn-anti mode. In complex 4, the Mn(pic)(2) fragments are joined to each other by double mu(1,1)-carboxylate bridges, forming a 2D layer structure. Complex 5 contains Mn4O4 square subunits which are connected by double mu-Cl bridges to form a grid-like 2D structure. The isonicotinate complex 6 has a zigzag chain structure containing mixed double mu-Cl and mu(1,3)-carboxylate bridges in a syn-syn mode. Protonation at the pyridyl-N position was found and identified by the IR and magnetic properties of 6. The participation of an oxidizing agent like MnO4- leads to complexes containing higher valent manganese (1, 2 and 7). The IR spectra of these complexes are discussed and found to be consistent with the structural features. The magnetic properties of complexes 4, 5 and 6 have been investigated. Antiferromagnetic coupling interactions were observed and satisfactory fitting results were obtained with J values ranging from -0.63 cm(-1) to -2.35 cm(-1). The magnetic parameters of these complexes, together with the parameters of other Mn complexes with comparable structures, are compared and discussed based on the bridging modes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).
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| 6. |
- Huang, D. U., et al.
(författare)
-
Synthesis, structural characterization and magnetic properties of 2-pyrazinecarboxylate manganese compounds Mn(pyz)(2)(H2O)(4) and MnCl(pyz)(H2O) (n) (pyz=2-pyrazinecarboxylate)
- 2003
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Ingår i: Inorganica Chimica Acta. - 0020-1693 .- 1873-3255. ; 353, s. 284-291
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Tidskriftsartikel (refereegranskat)abstract
- Two pyz complexes [Mn(pyz)(2)(H2O)(4)] (1) and [MnCl(pyz)(H2O)] (2) have been synthesized and structurally characterized. Complex 1 contains an eight-coordinate Mn(II) ion with square anti-prismatic geometry. The extensive intermolecular hydrogen-bonding interactions of O-carboxyl...H-O-aqua correlate the complex molecules, forming 2D polymeric layer structure. The structure of complex 2 contains 1D Mn/pyz chains, which link to each other by double mu(2)-Cl bridges to form 2D layer with Mn...Mn distance of 3.664 Angstrom. Hydrogen-bonding interactions of O-carboxyl...H-O-aqua are found between the layers to correlate the 2D layers to form a 3D framework. In addition, the variable temperature magnetic susceptibilities of complex 2 were measured and weak ferromagnetic exchange interactions between the neighboring magnetic species were found with J = 0.42 cm(-1).
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| 7. |
- Li, P., et al.
(författare)
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Influence of tertiary phosphanes on the coordination configurations and electrochemical properties of iron hydrogenase model complexes : Crystal structures of (mu-S2C3H6)Fe-2(CO)(6-n)L-n (L = PMe2Ph, n=1, 2; PPh3 P(OEt)(3), n=1)
- 2005
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :12, s. 2506-2513
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Tidskriftsartikel (refereegranskat)abstract
- A series of mono- and disubstituted diiron complexes [(mu-pdt)-Fe-2(CO)(5)L] [pdt = 1,3-propanedithiolato; L = PMe3 (2), PMe2Ph (3), PPh3 (4), P(OEt)(3) (5)] and [(mu-pdt)Fe-2(CO)(4)L-2] [L = PMe2Ph (6), PPh3 (7), P(OEt)3 (8)] were prepared as Fe-only hydrogenase-active-site models by controllable CO displacement of [(mu-pdt)Fe-2(CO)(6)] by tertiary phosphanes. The coordination configurations of 3-6 were characterized by X-ray crystallography. Disubstituted diiron complex 6 features an apical/apical coordination mode, instead of the typical transoid basal/basal configuration. The electrochemistry of 2-6 and 8 was studied by cyclic voltammetry to evaluate the effects of different tertiary phosphane ligands on the redox properties of the iron atoms of model complexes.
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| 8. |
- Ma, C. B., et al.
(författare)
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Structural transformation mediated by o-, m-, and p-phthalates from two to three dimensions for manganese/phthalate/4,4 '-bpy complexes (4,4 '-bpy=4,4 '-bipyridine)
- 2003
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Ingår i: New Journal of Chemistry. - : Royal Society of Chemistry (RSC). - 1144-0546 .- 1369-9261. ; 27:5, s. 890-894
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Tidskriftsartikel (refereegranskat)abstract
- Three isomers of o-, m-, and p-phthalate are used to link together Mn centres, resulting in [Mn(phth)(H2O)(x)](n) moieties ( phth = phthalate dianion) with single-chain, double-chain and sheet structures, respectively, which predetermine the extended structures derived from the crosslinkage of 4,4'-bipyridine, and show the influence of isomerism of the phthalate on topological changes of the final polymers from two dimensional (2D) single-layer, double-layer to 3D network architectures. These structural changes in topology are correlated with the differences in the magnetic and optical properties of the polymers.
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| 9. |
- Yang, X. C., et al.
(författare)
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The bromination mechanism of 1-aminoanthraquinone-2,4-disulfonic acid in sulfuric acid
- 2006
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Ingår i: Dyes and pigments. - : Elsevier BV. - 0143-7208 .- 1873-3743. ; 71:3, s. 231-235
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Tidskriftsartikel (refereegranskat)abstract
- I-Amino-4-bromoanthraquinotie-2-sulfoiiic acid (bromoamine acid) is an important intermediate for dyes. 1-Aminoanthraquinone2,4-disulfonic acid is the major impurity when 1-aminoanthraquinone is sulfonated in oleum to synthesize bromoamine acid. The mechanism of bromination of 1-aminoanthraquinone-2,4-disulfonic acid in sulfuric acid has been studied. It is proved that I-aminoanthraquinone-2,4-disulfonic acid undergoes de-sulfonation first to form 1-aminoanthraquinoine-2-sulfonic acid, and then bromination to form bromoamine acid. Based on this mechanism, a new optimal process for the synthesis of bromoamine acid is developed. In this way, bromoamine acid is afforded in high yield and good quality.
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| 10. |
- Zhang, X. F., et al.
(författare)
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catena-Poly (1,10-phenanthroline-kappa N-2,N ')manganese(II) -mu-L-tartrato-kappa O-4(1),O-2 : O-3,O-4 hexahydrate
- 2003
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Ingår i: Acta Crystallographica Section C. - 0108-2701 .- 1600-5759. ; 59, s. M402-M404
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Tidskriftsartikel (refereegranskat)abstract
- The title compound, {[Mn(C4H4O6)(C12H8N2)] . 6H(2)O}(n), has a linear chain structure containing monomeric [ Mn( C4H4O6)( C12H8N2)] repeat units. Each manganese ion is six-coordinate, with the two phenanthroline N atoms [Mn - N = 2.229 (2) and 2.235 (2) Angstrom] and four O atoms from two tartrate anions [Mn - O-COO = 2.1252 (19) and 2.1310 (19) Angstrom, and Mn - O-OH = 2.2404 (19) and 2.2424 (19) Angstrom] forming a seriously distorted octahedral coordination environment. Six water molecules exist outside every repeat unit as solvate molecules. Extensive hydrogen-bonding interactions and pi-pi stacking of the phenanthroline moieties exist between the chains.
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| 11. |
- Zhu, H. J., et al.
(författare)
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Preparation and structures of 6-and 7-coordinate salen-type zirconium complexes and their catalytic properties for oligomerization of ethylene
- 2005
-
Ingår i: Journal of Organometallic Chemistry. - : Elsevier BV. - 0022-328X .- 1872-8561. ; 690:17, s. 3929-3936
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Tidskriftsartikel (refereegranskat)abstract
- A series of salen-type zirconium complexes of the general formula LZrCl2 (L = N,N '-ethylenebis(salicylideneiminate), 3a; N,N '-ethylenebis(3,5-di-tert -butylsalicylideneiminate), 3b; N,N '-ethylenebis(5-methoxysalicylidenciminate), 3e; N,N '-o-phethylenebis(5-chlorosalicylideneiminate), 3d; N,N '-ethylenebis(5-nitrosalicylideneiminate), 3e; N,N '-o-phenylenebis(salicylideneiminate), 4a; N,N '-o-phenylenebis(3,5-di-tert-butylsalicylideneiminate), 4b; N,N '-o-phenylenebis(5-methoxysalicylideneiminate), 4c; N,N '-o-phenylenebis(5-chloro-salicylideneiminate), 4d) were prepared. The crystal structures of 6- and 7-coordinate zirconium complexes 4b and [4b center dot OCMe2] were determined by X-ray crystallography, which reveals that a salen-type zirconium complex possesses a labile coordination site on the Zr center with a relatively stable framework and that the coordination and the dissociation of O-donor molecules occur readily at this site. The catalytic properties of 3(a-e) and 4(a-d) were studied for ethylene oligomerization in combination with Et2AlCl as co-catalyst. Complex 3c featuring a methoxy-substituted salen ligand displayed higher activity than its analogous precursors having chloro and nitro groups as substituents. The catalytic reactions by 3(a-e) and 4(a-d) gave C-4-C-10 olefins and low-carbon linear (alpha-olefins in good selectivity.
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| 12. |
- Abrahamsson, M. L. A., et al.
(författare)
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Ruthenium-manganese complexes for artificial photosynthesis : Factors controlling intramolecular electron transfer and excited-state quenching reactions
- 2002
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 41:6, s. 1534-1544
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Tidskriftsartikel (refereegranskat)abstract
- Continuing our work toward a system mimicking the electron-transfer steps from manganese to P-680(+) in photosystem II (PS II), we report a series of ruthenium(II)-manganese(II) complexes that display intramolecular electron transfer from manganese(II) to photooxidized ruthenium(III). The electron-transfer rate constant (k(ET)) values span a large range, 1 X 10(5)-2 x 10(7) s(-1), and we have investigated different factors that are responsible for the variation. The reorganization energies determined experimentally (lambda = 1.5-2.0 eV) are larger than expected for solvent reorganization in complexes of similar size in polar solvents (typically lambda approximate to 1.0 eV). This result indicates that the inner reorganization energy is relatively large and, consequently, that at moderate driving force values manganese complexes are not fast donors. Both the type of manganese ligand and the link between the two metals are shown to be of great importance to the electron-transfer rate. In contrast, we show that the quenching of the excited state of the ruthenium(II) moiety by manganese(II) in this series of complexes mainly depends on the distance between the metals. However, by synthetically modifying the sensitizer so that the lowest metal-to-ligand charge transfer state was localized on the nonbridging ruthenium(II) ligands, we could reduce the quenching rate constant in one complex by a factor of 700 without changing the bridging ligand. Still, the manganese(II)-ruthenium (III) electrontransfer rate constant was not reduced. Consequently, the modification resulted in a complex with very favorable properties.
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| 13. |
- Chen, C. N., et al.
(författare)
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Aggregate manganese Schiff base moieties by terephthalate or acetate : Dinuclear manganese and trinuclear mixed metal Mn-2/Na complexes
- 2003
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 42:11, s. 3540-3548
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Tidskriftsartikel (refereegranskat)abstract
- A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn-2(mu-phth)(CH3OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn-2(mu-phth)(CH3OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn-2(mu-phth)(CH3OH)(H2O) (3), and (salen)(2)Mn-2(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH3OH)(NO3) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H{Mn2Na(salpn)(2)(mu-OAc)(2)(H2O)(2)}(OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. H-1 NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/0.12V has been assigned to the redox of Mn-2(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.
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| 14. |
- He, C. J., et al.
(författare)
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Advance in chemical mimic of Fe-only hydrogenase
- 2004
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Ingår i: Huaxue jinzhan. - 1005-281X. ; 16:2, s. 250-255
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Tidskriftsartikel (refereegranskat)abstract
- Hydrogenases are one of the important enzymes in many microorganisms, which can catalyze the reversible oxidation of hydrogen. They are classified into three categories according to their active metal centers, that is, Fe-only, [Ni-Fe] and metal free H-2 ases. This review introduces primarily the recent advances in structural investigation and chemical mimic of Fe-only H-2 ases.
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| 15. |
- Li, C. Y., et al.
(författare)
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A wide pH range optical sensing system based on a sol-gel encapsulated amino-functionalised corrole
- 2006
-
Ingår i: The Analyst. - : Royal Society of Chemistry (RSC). - 0003-2654 .- 1364-5528. ; 131:3, s. 388-393
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis of a new compound, 10-(4-aminophenyl)-5,15-dimesitylcorrole, and its application for the preparation of optical chemical pH sensors is described. The dye materials were immobilized in a sol - gel glass matrix and characterised upon exposure to aqueous buffer solutions. The response of the sensor is based on the fluorescence intensity changing of corrole owing to multiple steps of protonation and deprotonation. Due to its containing several proton sensitive centers, the 10-(4-aminophenyl)- 5,15-dimesitylcorrole based optode shows a wider response range toward pH than that of tetraphenylporphyrin (TPPH2) and 5,10,15-tris( pentafluorophenyl) corrole (H-3(tpfc)). It shows a linear pH response in the range of 2.17 - 10.30. The effect of the composition of the sensor membrane has been studied and the experimental conditions were optimized. The optode showed good reproducibility and reversibility, and common co-existing inorganic ions did not show obvious interference to its pH measurement.
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| 16. |
- Li, F., et al.
(författare)
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Mono- and binuclear complexes of iron(II) and iron(III) with an N4O ligand : synthesis, structures and catalytic properties in alkane oxidation
- 2006
-
Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; :20, s. 2427-2434
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Tidskriftsartikel (refereegranskat)abstract
- Three mononuclear iron complexes and one binuclear iron complex, [Fe(tpoen)Cl]center dot 0.5(Fe2OCl6) (1), [Fe(tpoen)Cl]PF6 (2), Fe(tpoen)Cl-3 (3) and [{Fe(tpoen)}(2)(mu-O)](ClO4)(4) (4) (tpoen = N-(2-pyridylmethoxyethyl)-N,N-bis(2-pyridylmethyl)amine), were synthesized as functional models of non-heme iron oxygenases. Crystallographic studies revealed that the Fe(II) center of 1 is in a pseudooctahedral environment with a pentadentate N4O ligand and a chloride ion trans to the oxygen atom. The Fe(III) center of 3 is ligated by three nitrogen atoms of tpoen and three chloride ions in a facial configuration. Each Fe(III) center of 4 is coordinated with four nitrogen atoms and an oxygen atom of tpoen with the Fe-O-Fe angle of 172.0(3) angstrom. Complexes 2, 3 and 4 catalysed the oxidation of cyclohexane with H2O2 in the total TNs of 24 - 36 with A/K ratios of 1.9-2.4. Under the same conditions they also catalysed both the oxidation of ethylbenzene to benzylic alcohol and acetobenzene with good activity (30-47 TN) and low selectivity (A/K 0.7), and the oxidation of adamantane with moderate activity (15-18 TN) and low regioselectivity (3 degrees/2 degrees 3.0-3.2). With mCPBA as oxidant the catalytic activities of 2, 3 and 4 increased 1.8 to 2.3-fold for the oxidation of cyclohexane and ethylbenzene and 6.3 to 7.5-fold for the oxidation of adamantane. Drastic enhancement of the regioselectivity was observed in the oxidation of adamantane (3 degrees/2 degrees 18.5-30.3).
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| 17. |
- Liu, X., et al.
(författare)
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Synthesis, characterization and some properties of amide-linked porphyrin-ruthenium(II) tris(bipyridine) complexes
- 2005
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Ingår i: Tetrahedron. - : Elsevier BV. - 0040-4020 .- 1464-5416. ; 61:23, s. 5655-5662
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Tidskriftsartikel (refereegranskat)abstract
- A new molecular dyad, comprised of a zinc-porphyrin and a ruthenium(II) tris(bipyridine) complex linked through an amide bond has been synthesized and characterized by H-1, C-13 NMR, UV-vis, mass-spectrometry and elemental analysis. The electrochemistry as well as the steady-state emission properties were investigated. The redox behavior of the dyad exhibits a favorable reversible characteristic. Substantial quenching of porphyrin emission was found when the Q hand of 5 and 5-Zn was selectively photoexcited. This observation suggests a quenching mechanism with possible intramolecular electron transfer or energy transfer between the Ru(bpy)(3) moiety and the porphyrin free-base or Zn porphyrin moieties.
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| 18. |
- Shi, F., et al.
(författare)
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Synthesis and spectral properties of a new ruthenium(II) tris-bipyridine with four ester groups and substituted phenol
- 2004
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Ingår i: Huaxue xuebao. - 0567-7351. ; 62:7, s. 713-719
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Tidskriftsartikel (refereegranskat)abstract
- A new ruthenium(II) complex (1) with four ester groups have been designed and synthesized, in which a phenol substituted by {[(2-hydroxy-3-(morpholin-4-ylmethyl)-5-tent-butylbenzyl) (pyridyl-2-methyl) amino]methyl} groups was covalently linked to ruthenium (II) tris-bipyridine. The structure of complex 1 was characterized by electrospray ionization mass spectrometer (ESI-MS) and 1D-NMR, 2D-NMR (gCOSY, HSQC and HMBC) spectra. The electrochemical and spectral properties were also studied. Introduction of the four carboxyl acid groups and the donor ligand tuned the spectra and the redox properties of compound 1. The MLCT transition was turned from 451 to 474 nm and the complex had long lifetime of the (MLCT)-M-3 state emission. Moreover, the oxidation potential of Ru3+/Ru2 + of compound 1 was similar to 360 mV higher than that of [Ru(bpy)(3)](2+) which would enhance the driving-force of electron transfer. These results showed that the compound 1 had proper redox potentials and was suitable for being used as photosensitizer of solar cell.
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| 19. |
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| 20. |
- Sun, S. G., et al.
(författare)
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Electrospray ionization mass spectrometry of rhenium(I) bipyridyl complexes
- 2003
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Ingår i: Youji huaxue. - 0253-2786. ; 23:10, s. 1135-1138
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Tidskriftsartikel (refereegranskat)abstract
- The electrospray ionization mass spectrometry (ESI-MS) of a series of rhenium(I) bipyridyl complexes [(4,4'-(COOEt)(2)-bPY)Re(CO)(3)RPF6], where bpy is 2,2'-bipyridine and R is pyridine, 4-methylpyridine, 4-hydroxypyridine, 4-aminopyridine or 10-(4-picolyl)phenothiazine (py-PTZ) was studied. The dissociation of the ligands (R) forms the fragment of [(4, 4'-( COOEt)(2)-bpy) Re (CO)3](+) at different voltages of in-source collision induced dissociation (CID). The dissociation tendency is in an order: pyridine > 4-methylpyridine > 4-hydroxypyridine > 4-aminopyridine > py-PTZ. It might be used to deduce the stability of these complexes when they are used as photosensitizers in solar cells.
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| 21. |
- Sun, S. G., et al.
(författare)
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Studies of a series of novel rhenium(I) bipyridyl dyes for solar cells
- 2005
-
Ingår i: Chinese Chemical Letters. - 1001-8417 .- 1878-5964. ; 16:5, s. 677-680
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Tidskriftsartikel (refereegranskat)abstract
- A series of novel rhenium(I) 2,2'-bipyridyl complexes [fac-Re(4,4'-di-COOEt-bpy)-(CO)(3)(Xpy)PF6], where bpy is 2,2'-bipyridine, py is pyridine and X is 3-methyl, 3-hydroxy, or 3-amino, were synthesized, their photophysical and electrochemical properties were studied. The Re(II/I) oxidation potentials decreased as the X group becomes more electron donating from H to 3-methyl, 3-hydroxy, or 3-amino, which might be a very convenient ways for adjusting the electron transfer driving force.
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| 22. |
- Sun, S. G., et al.
(författare)
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Studies on a series of rhenium(I) bipyridyl photosensitive dyes
- 2004
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Ingår i: Youji huaxue. - 0253-2786. ; 24:8, s. 953-956
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Tidskriftsartikel (refereegranskat)abstract
- A series of rhemium(I) 2,2'-bipyridyl complexes [fac-(4,4'-di-COOEt-bpy)Re(CO)(3)(Xpy)PF6] (bpy = 2, 2'-bipyridine; py = pyridine; X = 3-methyl, 3-hydroxy, 3-amino, H) were synthesized. Their electrochemical properties, ground state electronic spectra and emission spectra were studied in acetonitrile. As the X group became more electron donating from H to 3-methyl, 3-hydroxy or 3-amino, the Re(II/I) oxidation potentials declined, the MLCT absorption maximum of the complex was changed little, the emission maximum blue-shifted, and the emission intensity and the fluorescence lifetime were decreased.
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| 23. |
- Sun, S. G., et al.
(författare)
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Synthesis of a series of rhenium(I) bipyridyl complexes as photosensitive dyes
- 2004
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Ingår i: Gaodeng xuéxiào huàxué xuébào. - 0251-0790. ; 25:5, s. 820-822
-
Tidskriftsartikel (refereegranskat)abstract
- In order to study the effects of the substituted groups on the properties of the complexes, a series of rhenium ( I ) 2, 2'-bipyridyl complexes [fac- (4, 4'-di-COOEt-bpy) Re (CO)(3) (X-pyridine) PF6], where bpy is 2,2'-bipyridine and X is 4-methyl, 3-hydroxy, 4-hydroxy, 4-amino, or H, were synthesized with a yield more than 90%, and characterized by H-1 NMR, C-13 NMR, 2D-NMR (H-1-H-1 COSY, HMBC, HSQC), ESI-MS and HRMS. The delta(H) values on the X-pyridine ring were shifted to up-field in H-1 NMR and the MLCT absorbance maxima were red-shifted as the X groups became more electron-donating from H to 4-methyl, 4-hydroxy or 4-amino. The ESI-MS and FIRMS showed the mono-charged peaks and their isotopic peaks of the complexes. The absorption maximum of id(X=4-amino) is 20 nm longer than that of 1e(X=H). It might be used to broaden the absorption range of solar cells.
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| 24. |
- Sun, S. G., et al.
(författare)
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Synthesis of rhenium(I) bipyridyl and ruthenium(II) tris-bipyridyl photosensitive dyes used for solar cells
- 2004
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Ingår i: Gaodeng xuéxiào huàxué xuébào. - 0251-0790. ; 25:1, s. 67-70
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Tidskriftsartikel (refereegranskat)abstract
- There has been a growing effort to convert solar energy into electricity in recent years. In order to get a stable solar cell system and acquire a high incident photon-to-current conversion efficiency(IPCE), two novel rhenium(I) bipyridyl and ruthenium(II) tris-bipyridyl photosensitive dyes were synthesized, the ethoxycarbonyl group in the dyes could be employed for covalently linking to the surface of the nanostructured TiO2. Their structures, photophysical and electrochemical properties were studied. The UV-Vis absorption maxima were 382 and 476 nm; emission maxima were 622 and 672 nm, respectively. The Re(I/II) oxidation potential is significantly positive than that of Ru(II/III) which provides a larger driving force for electron transfer. The results show that they both have proper redox potentials, enough stability and are suitable for being used as photosensitizers of solar cells.
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| 25. |
- Sun, S. G., et al.
(författare)
-
Synthesis of two novel rhenium(I) bipyridyl photosensitive dyes
- 2004
-
Ingår i: Chinese Chemical Letters. - 1001-8417 .- 1878-5964. ; 15:8, s. 965-968
-
Tidskriftsartikel (refereegranskat)abstract
- Two novel rhenium(I) 2, 2'-bipyridyl complexes, [(4,4'-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4'-di-COOEt-bipy) Re (CO)(3) (NCS)], a model complex [(4,4'-di-COOEt-bipy) Re (CO)(3) (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN.
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| 26. |
- Wang, M., et al.
(författare)
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Metal-organic frameworks (ZIF-67) as efficient cocatalysts for photocatalytic reduction of CO2 : The role of the morphology effect
- 2018
-
Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 6:11, s. 4768-4775
-
Tidskriftsartikel (refereegranskat)abstract
- Metal-organic frameworks (MOFs), ZIF-67, with different morphologies were synthesized via a solvent-induced method at room temperature. The photocatalytic performances towards the reduction of CO2 were evaluated by using ZIF-67 materials as cocatalysts cooperating with a ruthenium-based complex as the photosensitizer. It has been demonstrated that the two-dimensional ZIF-67 with a leaf-like morphology exhibited the best photocatalytic activity and stability due to the highest CO2 adsorption capability and efficient electron transfer from the excited [Ru(bpy)3]2+ to ZIF-67.
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| 27. |
- Wang, M., et al.
(författare)
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Preparation, characterization and catalytic oxidation properties of tris 2-(2-pyridyl)benzimidazole iron(II) complexes
- 2004
-
Ingår i: Applied organometallic chemistry. - : Wiley. - 0268-2605 .- 1099-0739. ; 18:6, s. 277-281
-
Tidskriftsartikel (refereegranskat)abstract
- Complexes [Fe(Hpbi)(3)](ClO4)(2) (1) and [Fe(Hpbi)(3)](SbF6)(2) (2) (Hpbi = 2-(2-pyridyl)benzimidazole) were prepared by a modified method and characterized by IR, H-1 and C-13 NMR, mass spectrometry, electron paramagnetic resonance spectra and elemental analysis. The catalytic activities of 1 and 2 were evaluated for the oxidation of cyclohexene, cyclohexane, ethylbenzene and adamantane with tert-butylhydroperoxide or H2O2 as oxidant, and the results were compared with the properties of their analogue [Fe(bpy)(3)](SbF6)(2) (3). Complexes 1 and 2 both afforded the ketonization product for the oxidation of ethylbenzene and the hydroxylation product for adamantane.
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| 28. |
- Wang, M., et al.
(författare)
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Salen-type zirconium complexes with a labile coordination site and a robust skeleton : crystal structure of (t-Bu-4-salen)ZrCl2(H2O)
- 2004
-
Ingår i: Journal of Organometallic Chemistry. - : Elsevier BV. - 0022-328X .- 1872-8561. ; 689:7, s. 1212-1217
-
Tidskriftsartikel (refereegranskat)abstract
- Treatment of LZrCl2 (L - N, N'-ethylenebis(3,5-di-tert-butylsalicylideneiminato) (1), N, N'-o-phenylenebis(3,5-di-tert-butylsalicylideneiminato) (2)), which is an effective catalyst precursor for ethylene oligomerization, with 1.5 equiv of water in toluene afforded H2O-coordinating salen-type zirconium complexes [LZrCl2(H2O)]. The effects of the content of H2O and the temperature on the equilibrium of association and disassociation of H2O molecule in [LZrCl2(H2O)(n)] (n = 0, 1) were studied in solution (CDCl3) by H-1 NMR spectroscopy. The crystal and molecular structure of [1(H2O)] was determined by X-ray diffraction analysis, which revealed that a herringbone supramolecular assembly was constructed in the crystalline state of [1(H2O)], stacked by the intermolecular hydrogen bonds between the OH group of the coordinating H2O and one of the chloride ligands.
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| 29. |
- Yang, X. C., et al.
(författare)
-
Axial ligand exchange reaction on ruthenium phthalocyanines
- 2005
-
Ingår i: Journal of Porphyrins and Phthalocyanines. - 1088-4246 .- 1099-1409. ; 9:4, s. 248-255
-
Tidskriftsartikel (refereegranskat)abstract
- Bis(4-methylpyridine)phthalocyaninato ruthenium(II) has been synthesized. It was proved by single-crystal X-ray diffraction that the central Ru(II) atom is bonded to six N atoms in an elongated octahedral configuration, and the axial ligands have a significantly longer Ru-N bond distance, 2.101(4) angstrom, than the independent pyrrol Ru-N bond, 1.99 angstrom. Therefore, the axial ligands can be exchanged by other ligands. The ligand exchange reactions with diethyl pyridyl-4-phosphonate and diethyl pyridylmethyl-4-phosphonate were studied in high boiling-point solvents at elevated temperatures, ca 160 degrees C. Mono-ligand as well as double-ligand replaced complexes were obtained. The complexes have been isolated by column chromatography. These complexes have potential applications, such as in dye sensitized solar cells.
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| 30. |
- Zhang, R., et al.
(författare)
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Electrospray ionization mass spectrometry studies of rhenium(I) bipyridyl complexes
- 2004
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Ingår i: European journal of mass spectrometry. - : SAGE Publications. - 1469-0667 .- 1751-6838. ; 10:5, s. 599-603
-
Tidskriftsartikel (refereegranskat)abstract
- Electrospray ionization mass spectrometry has been employed to study the formation of fragment ions from a series of rhenium(I) bipyridyl complexes [(4,4'-di-(COOEt)(2)-bpy) Re(CO)(3)XPyPF6], where bpy is 2,2'-bipyridine, Py is pyridine and X is H, 4-methyl, 3-methyl, 4-hydroxyl, 3-hydroxyl, 4-amino, or 3-amino of the pyridine ligand. The effects of substituents (X) on the stability of the complexes has been investigated with the increase of fragmentor voltages. For different X substitutents, the stability of the complexes increases as X becomes more electron-donating from H to CH3, OH and NH2. For the same substitutent, the p-substituted pyridines have a stronger stabilizing effect than the corresponding m-substituted ones. Ligand exchange reaction was found in acetonitrile, where the pyridine ligand has been replaced by the solvent, indicated by the formation of [M - PF6 - XPy + MeCN](+) in the fragmentation.
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| 31. |
- Zhu, H. J., et al.
(författare)
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Coordination polyhedra of eight-coordinate zirconium complexes and a network built up by crisscross Cl...Cl contacts
- 2005
-
Ingår i: Transition metal chemistry (Weinheim). - : Springer Science and Business Media LLC. - 0340-4285 .- 1572-901X. ; 30:5, s. 517-522
-
Tidskriftsartikel (refereegranskat)abstract
- Two bis(quadridentate) eight-coordinate zirconium complexes, Zr(5-Cldse)(2) (1) [5-Cldse = N,N'-di(5-chlorosalicylidene)ethylenediamino] and Zr(pida)(2) (2) [pida = N-(2-pyridylmethyl) iminodiacetato], have been prepared and crystallographically characterized. A distorted dodecahedron of N4O4 atoms has been found for the zirconium(IV) center of complexes (1) and (2). A network is constructed in the crystalline state of (1) by crisscross intermolecular Cl...Cl contacts (3.45 and 3.43 angstrom), which are shorter than the sum of spherical van der Waals radii (3.50 angstrom).
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| 32. |
- Abrahamsson, Maria, et al.
(författare)
-
A new strategy for the improvement of photophysical properties in ruthenium(II) polypyridyl complexes. Synthesis and photophysical and electrochemical characterization of six mononuclear ruthenium(II) bisterpyridine-type complexes
- 2005
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 44:9, s. 3215-3225
-
Tidskriftsartikel (refereegranskat)abstract
- The synthesis and characterization of six ruthenium(II) bistridentate polypyridyl complexes is described. These were designed on the basis of a new approach to increase the excited-state lifetime of ruthenium(II) bisterpyridine-type complexes. By the use of a bipyridylpyridyl methane ligand in place of terpyridine, the coordination environment of the metal ion becomes nearly octahedral and the rate of deactivation via ligand-field (i.e., metal-centered) states was reduced as shown by temperature-dependent emission lifetime studies. Still, the possibility to make quasi-linear donor-ruthenium-acceptor triads is maintained in the complexes. The most promising complex shows an excited-state lifet me of tau = 15 ns in alcohol solutions at room temperature, which should be compared to a lifetime of tau = 0.25 ns for [Ru(tpy)(2)](2+). The X-ray structure of the new complex indeed shows a more octahedral geometry than that of [Ru(tpy)(2)](2+). Most importantly, the high excited-state energy was retained, and thus, so was the potential high reactivity of the excited complex, which has not been the case with previously published strategies based on bistridentate complexes.
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| 33. |
- An, J., et al.
(författare)
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Stable and efficient PbS colloidal quantum dot solar cells incorporating low-temperature processed carbon paste counter electrodes
- 2017
-
Ingår i: Solar Energy. - : Elsevier. - 0038-092X .- 1471-1257. ; 158, s. 28-33
-
Tidskriftsartikel (refereegranskat)abstract
- Colloidal quantum dot (CQD) solar cells with a ZnO/PbS-TBAI/PbS-EDT/carbon structure were prepared using a solution processing technique. A commercially available carbon paste that was processed at low-temperatures was used as a counter electrode in place of expensive noble metals, such as Au or Ag, which are used in traditional PbS CQD solar cells. These CQD solar cells exhibited remarkable photovoltaic performance with a short circuit density (Jsc) of 25.6 mA/cm2, an open circuit voltage (Voc) of 0.45 V, a fill factor (FF) of 51.8% and a power conversion efficiency (PCE) as high as 5.9%. A reference device with an Au counter electrode had a PCE of 6.0%. The PCE of the carbon-containing CQD solar cell remained stable for 180 days when tested in ambient atmosphere, while the PCE of the Au-containing CQD solar cell lost 48.3% of its original value. Electrochemical impedance spectroscopy (EIS) demonstrated that holes within the PbS CQD were effectively transported to the carbon counter electrode.
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| 34. |
- Berg, K. E., et al.
(författare)
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Covalently linked ruthenium(II)-manganese(II) complexes : Distance dependence of quenching and electron transfer
- 2001
-
Ingår i: European Journal of Inorganic Chemistry. - 1434-1948 .- 1099-1948. ; 2001:4, s. 1019-1029
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Tidskriftsartikel (refereegranskat)abstract
- Continuing our development of artificial models for photosystem II in green plants, a series of compounds have been prepared in which a RU(bpy)(3)(2+) photosensitizer is covalently Linked to a manganese(II) electron donor. In addition to a trispicolylamine Ligand, two other manganese Ligands, dipicolylamine and aminodiacetic acid, have been introduced in order to study Ligands that are appropriate for the construction of manganese dimers with open coordination sites for the binding of water. Coordination equilibria of the manganese ions were monitored by EPR. The interactions between the ruthenium and manganese moieties were probed by flash photolysis, cyclic voltammetry and steady-state and time-resolved emission measurements. The quenching of the Ru-II excited state by Mn-II was found to be rapid in complexes with short Ru-Mn distances. Nevertheless, each Run species could be photo-oxidized by bimolecular quenching with methylviologen, and the subsequent electron transfer from Mn-II to Ru-III could be monitored.
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| 35. |
- Borgstrom, M., et al.
(författare)
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Electron donor-acceptor dyads and triads based on tris(bipyridine)ruthenium(II) and benzoquinone : Synthesis, characterization, and photoinduced electron transfer reactions
- 2003
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 42:17, s. 5173-5184
-
Tidskriftsartikel (refereegranskat)abstract
- Two electron donor-acceptor triads based on a benzoquinone acceptor linked to a light absorbing [Ru(bpy)(3)](2+) complex have been synthesized. In triad 6 (denoted Ru-II-BQ-Co-III), a [Co(bpy)(3)](3+) complex, a potential secondary acceptor, was linked to the quinone. In the other triad, 8 (denoted PTZ-Ru-II-BQ), a phenothiazine donor was linked to the ruthenium moiety. The corresponding dyads Ru-II-BQ (4) and PTZ-Ru-II (9) were prepared for comparison. Upon light excitation in the visible band of the ruthenium moiety, electron transfer to the quinone occurred with a rate constant k(1) = 5 x 10(9) s(-1) (tau(1) = 200 ps) in all the quinone containing complexes. Recombination to the ground state followed, with a rate constant k(b) similar to 4.5 x 10(8) s(-1) (tau(b) similar to 2.2 ns), for both Ru-II-BQ and Ru-II-BQ-Co-III with no indication of a charge shift to generate the reduced Coll moiety. In the PTZ-Ru-II-BQ triad, however, the initial charge separation was followed by a rapid (k > 5 x 10(9) s(-1)) electron transfer from the phenothiazine moiety to give the fairly long-lived PTZ(.+)-Ru-II-BQ(.-) state (tau = 80 ns) in unusually high yield for a [Ru(bPY)(3)](2+)- based triad (> 90%), that lies at DeltaGdegrees = 1.32 eV relative to the ground state. Unfortunately, this triad turned out to be rather photolabile. Interestingly, coupling between the oxidized PTZ(.+) and the BQ(.-) moieties seemed to occur. This discouraged further extension to incorporate more redox active units. Finally, in the dyad PTZ-Ru-II a reversible, near isoergonic electron transfer was observed on excitation. Thus, a quasiequilibrium was established with an observed time constant of 7 ns, with ca. 82% of the population in the PTZ-Ru-*(II) state and 18% in the PTZ(.+)Ru(II)(bpy(.-)) state. These states decayed in parallel with an observed lifetime of 90 ns. The initial electron transfer to form the PTZ(.+)-Ru-II(bpy(.-)) state was thus faster than what would have been inferred from the Ru-*(II) emission decay (tau = 90 ns). This result suggests that reports for related PTZ-Ru-II and PTZ-Ru-II-acceptor complexes in the literature might need to be reconsidered.
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| 36. |
- Boschloo, G., et al.
(författare)
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A comparative study of a polyene-diphenylaniline dye and Ru(dcbpy)(2)(NCS)(2) in electrolyte-based and solid-state dye-sensitized solar cells
- 2008
-
Ingår i: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 516:20, s. 7214-7217
-
Tidskriftsartikel (refereegranskat)abstract
- A small organic sensitizer, the polyene-diphenylaniline dye D5, was compared with the standard sensitizer N719 (Ru(dcbPY)(2)(NCS)(2)) in a dyesensitized solar cell investigation. In solar cells with relatively thin layers of mesoporous TiO2 (< 3 mu m) D5 outperformed N719 because of its high extinction coefficient. D5 showed also better performance than N719 in the case of sensitization of mesoporous ZnO. In solid-state solar cells, where the iodide/triiodide electrolyte was replaced by an amorphous hole conductor (spiro-OMeTAD), D5 gave promising preliminary results. The hole conductivity, observed in monolayers of D5 adsorbed at TiO2, may possibly lead to improved performance in such cells.
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| 37. |
- Canton, S. E., et al.
(författare)
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Watching the dynamics of electrons and atoms at work in solar energy conversion
- 2015
-
Ingår i: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 185, s. 51-68
-
Tidskriftsartikel (refereegranskat)abstract
- The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium-cobalt dyads, which belong to the large family of donor-bridge-acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray
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| 38. |
- Chen, C., et al.
(författare)
-
Boosting Electrocatalytic Water Oxidation by Creating Defects and Lattice-Oxygen Active Sites on Ni-Fe Nanosheets
- 2020
-
Ingår i: ChemSusChem. - : Wiley-VCH Verlag. - 1864-5631 .- 1864-564X. ; 13:18, s. 5067-5072
-
Tidskriftsartikel (refereegranskat)abstract
- Layered nickel-iron oxide/hydroxide nanosheets have proven to be the most efficient catalyst for the water oxidation reaction. Introducing structural defects to the nanosheets is a particularly attractive method for increasing the number of active sites and tailoring the intrinsic electronic properties. Herein, defects were introduced on Ni−Fe nanosheets through sequentially electrodoping and dedoping the surface of the material with tetramethylammonium ions. The as-prepared defect-rich Ni−Fe nanosheets showed an enhanced catalytic performance for the oxygen evolution reaction (OER) compared with conventional NiFe layered double hydroxides (LDHs), exhibiting an overpotential of only 172 mV at the current density of 10 mA cm−2. The relationship between pH and OER activity indicated that the lattice oxygens participated in the catalytic OER process as active sites. This work provides new insights into the understanding of the structure-activity relationship of layered materials and helps to develop new methods to implement defects on such frameworks aided by organic molecules.
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| 39. |
- Chen, C., et al.
(författare)
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Molecular engineering of ionic type perylenediimide dimer-based electron transport materials for efficient planar perovskite solar cells
- 2018
-
Ingår i: Materials Today Energy. - : Elsevier Ltd. - 2468-6069. ; 9, s. 264-270
-
Tidskriftsartikel (refereegranskat)abstract
- The main of this work is to overcome the drawbacks of the traditional fullerene derivatives used as electron transport materials (ETMs) for perovskite solar cells (PSCs). Herein, a new strategy to design non-fullerene ETMs is presented by molecular engineering to include charged moieties in the ETM. The designed ETM FA2+-PDI2 is intrinsically ionic and the incorporated counter ions in FA2+-PDI2 significantly increase the electron conductivity and improve the film formation properties. Through careful device optimization, PSCs based on the ionic ETM FA2+-PDI2 exhibit an impressive average power conversion efficiency (PCE) of 17.0%, which is comparable to the PSC based on PC61BM (17.5%). The superior photovoltaic performance can be attributed to efficient electron extraction and effective electron transfer in the PSCs. This work provides important insights regarding the future design of new and efficient non-fullerene ETMs for PSCs.
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| 40. |
- Chen, Y. G., et al.
(författare)
-
Synthesis and property of a chiral salen Mn(III) complex covalently linked to an Ru(II) tris(bipyridyl) photosensitizer
- 2005
-
Ingår i: Inorganic Chemistry Communications. - : Elsevier BV. - 1387-7003 .- 1879-0259. ; 8:7, s. 606-609
-
Tidskriftsartikel (refereegranskat)abstract
- A catalyst-photo sensitizer binuclear Mn(III)Ru(II) complex was prepared, in which the catalyst moiety of the Mn(III) unit with a chiral pyrrolidine salen ligand was covalently linked to a photosensitizer of the Ru(II) tris(bipyridyl) fragment. The electrochemical and photophysical properties of the Mn(III)Ru(II) complex were studied.
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| 41. |
- Chen, Y. G., et al.
(författare)
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Synthesis of chiral salen Mn(III) complexes covalently linked to Re(I)-based photosensitizers
- 2006
-
Ingår i: Journal of coordination chemistry (Print). - : Informa UK Limited. - 0095-8972 .- 1029-0389. ; 59:5, s. 475-484
-
Tidskriftsartikel (refereegranskat)abstract
- Two Mn(III)Re(I) binuclear complexes were prepared as catalyst-photosensitizer models, in which the chiral pyrrolidine salen Mn(III) unit was covalently bonded to an Re(I) bipyridyl carbonyl moiety via a carboxamide linkage. The spectral and electrochemical properties of the Mn(III)Re(I) complexes were studied.
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| 42. |
- Cheng, Ming, et al.
(författare)
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Phenoxazine-based small molecule material for efficient perovskite solar cells and bulk heterojunction organic solar cells
- 2015
-
Ingår i: Advanced Energy Materials. - : Wiley. - 1614-6832 .- 1614-6840. ; 5:8
-
Tidskriftsartikel (refereegranskat)abstract
- The phenoxazine-based acceptor-donor-acceptor structured small-molecule material M1 is used either as a hole-transport material in (CH3NH3)PbI3-perovskite-based solar cells or as photoactive donor material in bulk heterojunction organic solar cells. Excellent power conversion efficiencies of 13.2% and 6.9% are achieved in these two types of photovoltaic devices, respectively.
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| 43. |
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| 44. |
- Fryxelius, J., et al.
(författare)
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Synthesis and redox properties of a meso-tris(4-nitrophenyl) corrolato Mn(III) complex
- 2005
-
Ingår i: Journal of Porphyrins and Phthalocyanines. - 1088-4246 .- 1099-1409. ; 9:6, s. 379-386
-
Tidskriftsartikel (refereegranskat)abstract
- The Mn complexated corrole [T(4-NO2P)Corr]Mn(py) (3) has been prepared (py = pyridine) where [T(4-NO2P)Corr] is the trianion of the electron-poor 5,10,15-tris(4-nitrophenyl)-corrole (1). The preparation of 3 includes a new synthetic method to form the corrole ligand 1 in a two-step synthesis. The Mn(III) complex gives a parallel mode EPR signal centered around g = 8.2 with six distinct hyperfine lines (A(parallel to) = 139 x 10(-4) cm(-1)). Electrochemically 3 undergoes one reversible oxidation (E-1/2 = 0.12 V vs Fc) and two reversible reductions (E-1/2 = -1.45, -1.61 V). The oxidation is metal-centered and the product has been characterized by EPR spectroscopy as an S = 3/2 Mn(IV) species with no indication for oxidation of the macrocycle. The reductions of complex 3 are ligand based, and at the potential of the second reduction step a stable nitrogen centered radical with g = 2.0055 is generated. Chemical oxidation of 3 by iodosobenzene yields a Mn(IV) complex and epoxidation of cis-stilbene is not catalyzed by the Mn complex.
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| 45. |
- Ghanem, Raed, et al.
(författare)
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Light-driven tyrosine radical formation in a ruthenium-tyrosine complex attached to nanoparticle TiO2
- 2002
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 41:24, s. 6258-6266
-
Tidskriftsartikel (refereegranskat)abstract
- We demonstrate a possibility of multistep electron transfer in a supramolecular complex adsorbed on the surface of nanocrystalline TiO2. The complex mimics the function of the tyrosinez and chlorophyll unit P-680 in natural photosystem II (PSII). A ruthenium(II) tris(bipyridyl) complex covalently linked to a L-tyrosine ethyl ester through an amide bond was attached to the surface of nanocrystalline TiO2 via carboxylic acid groups linked to the bpy ligands. Synthesis and characterization of this complex are described. Excitation (450 nm) of the complex promotes an electron to a metal-to-ligand charge-transfer (MLCT) excited state, from which the electron is injected into TiO2. The photogeneration of Ru(III) is followed by an intramolecular electron transfer from tyrosine to Ru(III), regenerating the photosensitizer Ru(II) and forming the tyrosyl radical. The tyrosyl radical is formed in less than 5 us with a yield of 15%. This rather low yield is a result of a fast back electron transfer reaction from the nanocrystalline TiO2 to the photogenerated Ru(III).
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| 46. |
- Guo, X. W., et al.
(författare)
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Effects of SiO2/Al2O3, MgO modification and hydrothermal treatment on the catalytic activity of HZSM-5 zeolites in the methylation of 4-methylbiphenyl with methanol
- 2004
-
Ingår i: Applied Catalysis A. - : Elsevier BV. - 0926-860X .- 1873-3875. ; 261:2, s. 183-189
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Tidskriftsartikel (refereegranskat)abstract
- The objective of this work is to study the effects Of SiO2/Al2O3 of HZSM-5, MgO modification and hydrothermal treatment on methylation of 4-methylbiphenyl (4-MBP) with methanol under fixed-bed down-flow conditions. The results show that, with an increase in the SiO2/Al2O3 of HZSM-5 (from 50 to 150, molar ratio), the selectivity to 4,4'-dimethylbiphenyl (4,4'-DMBP) increases from 25 to 79%. MgO modification also increases the selectivity to 4,4'-DMBP, but leads as well to low catalyst activity and rapid deactivation. Hydrothermal treatment not only increases the selectivity, but also improves the stability. When CBV1502 (SiO2/Al2O3 = 150) catalyst was hydrothermally treated at 500degreesC, the selectivity to 4,4'-DMBP increased to 85%. The selectivity to 4,4'-DMBP was further improved to about 90% by the increasing in the amount of mesitylene in the feed as solvent.
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| 47. |
- Guo, X. W., et al.
(författare)
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Methylation of 4-methylbiphenyl with methanol over metal oxide-modified HZSM-5 zeolite catalysts
- 2003
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Ingår i: Cuihuà xuébào. - 0253-9837 .- 1872-2067. ; 24:5, s. 333-337
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Tidskriftsartikel (refereegranskat)abstract
- A series of HZSM-5 zeolite catalysts modifed with metal oxides (MgO, CaO, SrO, BaO, ZnO, La2O3 and CeO2) were prepared by impregnation method and characterized by XRD, TPD and N-2-adsorption. Methylation of 4-methylbiphenyl (4-MBP) with methanol to 4,4'-dimethylbiphenyl (4,4'-DMBP) was carried out over the prepared catalysts under fixed-bed down-flow conditions. The results showed that the MgO-modified HZSM-5 can significantly improve the selectivity for target product 4,4'-DMBP (up to 80 % vs only 13 % over the parent HZSM-5). The effects of metal oxides on 4,4'-DMBP selectivity are arranged in the following order: MgO>SrOapproximate toZnOapproximate toCaOapproximate toLa(2)O(3)>BaO>CeO2. The effects of MgO contents, precursor-salt types, and loading methods were further investigated, and the results revealed that during 4-MBP conversion, proper MgO loading (5.6 %) can be more effective, and the ion-exchange methed is much better than the impregnation method. However, it is difficult to get higher metal oxide loading by using the ion-exchange method. The high selectivity over HZSM-5 modified with MgO largely results from the depression of 4,4-DMBP second reactions such as isomerization, dealkylation and alkylation, as demonstrated by the reaction of 4,4'-DMBP as reactant over MgO/ZSM-5 catalyst and HZSM-5 zeolite.
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| 48. |
- Guo, X. W., et al.
(författare)
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Shape-selective methylation of 4-methylbiphenyl to 4,4 '-dimethylbiphenyl over zeolite HZSM-5 modified with metal oxides of MgO, CaO, SrO, BaO, and ZnO
- 2003
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Ingår i: Catalysis Letters. - 1011-372X .- 1572-879X. ; 87:02-jan, s. 25-29
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Tidskriftsartikel (refereegranskat)abstract
- A series of ZSM-5 samples modified with metal oxides MO(M = Mg, Ca, Sr, Ba and Zn) were employed for the alkylation of 4-methylbiphenyl (4-MBP) with methanol to 4,4'-dimethylbiphenyl (4,4'-DMBP) under fixed-bed down-flow conditions. The methylation results showed that the use of basic metal oxides can effectively enhance the selectivity to the target product 4,4'-DMBP. MgO is the most effective modifier among the metal oxides used and it can improve selectivity to 4,4'-DMBP up to 80% as compared to only 13% over the parent zeolite HZSM-5. The modi. cation effectiveness of metal oxides on 4,4'-DMBP selectivity can be arranged in the order MgO> SrO similar to ZnO similar to CaO> BaO. The optimization of MgO modi. cation through the content, salt types and loading methods revealed that proper MgO loading (5.6 wt%) can be more effective, and the impregnation method is much better than ion exchange. The correlation of physicochemical properties (TPD, TGA, chemical analysis and chemical adsorption, etc.) of the modified HZSM-5 with the catalytic data showed that the high selectivity over ZSM-5 modified with MgO largely results from the effective suppression of 4,4'-DMBP secondary reactions such as isomerization, dealkylation and alkylation.
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| 49. |
- Guo, Y., et al.
(författare)
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A Phenanthrocarbazole-Based Dopant-Free Hole-Transport Polymer with Noncovalent Conformational Locking for Efficient Perovskite Solar Cells
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:6
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Tidskriftsartikel (refereegranskat)abstract
- Adequate hole mobility is the prerequisite for dopant-free polymeric hole-transport materials (HTMs). Constraining the configurational variation of polymer chains to afford a rigid and planar backbone can reduce unfavorable reorganization energy and improve hole mobility. Herein, a noncovalent conformational locking via S–O secondary interaction is exploited in a phenanthrocarbazole (PC) based polymeric HTM, PC6, to fix the molecular geometry and significantly reduce reorganization energy. Systematic studies on structurally explicit repeats to targeted polymers reveals that the broad and planar backbone of PC remarkably enhances π–π stacking of adjacent polymers, facilitating intermolecular charge transfer greatly. The inserted “Lewis soft” oxygen atoms passivate the trap sites efficiently at the perovskite/HTM interface and further suppress interfacial recombination. Consequently, a PSC employing PC6 as a dopant-free HTM offers an excellent power conversion efficiency of 22.2 % and significantly improved longevity, rendering it as one of the best PSCs based on dopant-free HTMs.
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| 50. |
- Hammarstrom, L., et al.
(författare)
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A biomimetic approach to artificial photosynthesis : Ru(II)-polypyridine photo-sensitisers linked to tyrosine and manganese electron donors
- 2001
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - 1386-1425 .- 1873-3557. ; 57:11, s. 2145-2160
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Forskningsöversikt (refereegranskat)abstract
- The paper describes recent advances towards the construction of functional rr mics of the oxygen evolving complex in photosystem II (PSII) that are coupled to photoinduced charge separation. Some key principles of PSII and artificial systems for light-induced charge accumulation are discussed. Systems are described where biomimetic electron donors - manganese complexes and tyrosine - have been linked to a Ru(II)-polypyridine photosensitiser. Oxidation of the donors by intramolecular electron transfer from the photo-oxidised Ru(III) complex has been studied using optical flash photolysis and EPR experiments. A step-wise electron transfer Mn-2(III,III) --> tyrosine --> Ru(III) has been demonstrated, in analogy to the reaction on the donor side of PSII Electron transfer from the tyrosine to Ru(III) was coupled to tyrosine deprotonation. This resulted in a large reorganisation energy and thus a slow reaction rate, unless the tyrosine was hydrogen bonded or already deprotonated. A comparison with analogous reactions in PSH is made. Finally, light-induced oxidation of a manganese dimer linked to a Ru(II)-photosensitiser has been observed. Preliminary results suggest the possibility of photo-oxidising manganese dimers in several steps, which is an important advancement towards water oxidation.
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