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Tatsuya Nabeshima - One of the best experts on this subject based on the ideXlab platform.
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Heterodinuclear Group 13 Element Complexes of N4O6-Type Dipyrrin with an Unsymmetrical Twisted Structure
'Wiley', 2019Co-Authors: 松岡 亮太, Takashi Nakamura, Makoto Saikawa, Ryota Matsuoka, 鍋島 達弥, Takumu Noda, Tatsuya NabeshimaAbstract:Heterodinuclear group 13 element complexes of an N4O6‐type Dipyrrin cyclic dimer were synthesized by the stepwise reaction with boron and group 13 elements (Al, Ga, and In). The macrocycles have a new type of unsymmetrical twisted (pseudo‐figure‐of‐eight) structure
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A Conformationally Flexible Macrocyclic Dipyrrin Tetramer and Its Unsymmetrically Twisted Luminescent Zinc(II) Complex.
Inorganic chemistry, 2018Co-Authors: Tomohiro Hojo, Ryota Matsuoka, Tatsuya NabeshimaAbstract:A macrocyclic Dipyrrin tetramer containing flexible m-phenylene linkages and its tetranuclear zinc(II) complex were synthesized. The obtained complex has an unsymmetrical figure-of-eight structure because of the conformational flexibility of the macrocyclic framework. The first μ-hydroxo- and μ-acetato-bridged dinuclear zinc(II) Dipyrrin complex structure is realized in the twisted macrocyclic complex. Furthermore, the complex exhibited an efficient emission in toluene and chloroform.
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functional supramolecular architectures of Dipyrrin complexes
Frontiers in Chemistry, 2018Co-Authors: Ryota Matsuoka, Tatsuya NabeshimaAbstract:Dynamic formation of self-assemblies from molecular components is a useful and efficient way to produce molecular and supramolecular architectures with sophisticated functions. The labile coordination bond and dynamic covalent bond as a reversible bond have often been used to create a well-organized supramolecular self-assembly. In order to realize sophisticated novel functions of the supramolecular self-assemblies, Dipyrrin complexes have recently been employed as a functional unit and incorporated into the supramolecular architectures because of their outstanding properties and functions such as a high photostability and strong light absorption/emission. This review article summarizes recent development in functional supramolecular architectures of the Dipyrrin complexes produced by coordination to a metal ion and dynamic covalent bond formation. We first describe the synthesis and unique functions of a series of discrete supramolecular architectures: helicates, macrocycles, and cages. The polymeric supramolecular self-assemblies with 1D, 2D, and 3D structures are then introduced as a functional infinite supramolecular architecture.
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Synthesis and Unique Optical Properties of Selenophenyl BODIPYs and Their Linear Oligomers
2018Co-Authors: Daisuke Taguchi, Takashi Nakamura, Hiroaki Horiuchi, Makoto Saikawa, Tatsuya NabeshimaAbstract:A series of selenophene-substituted boron-Dipyrrin (BODIPY) monomers and selenophene-linked BODIPY oligomers was synthesized. The synthesized BODIPYs show good absorption/emission properties in the red to near-infrared region. Furthermore, some of the selenophenyl BODIPYs are not only useful fluorophores but also good photosensitizers to produce singlet oxygen
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A Conformationally Flexible Macrocyclic Dipyrrin Tetramer and Its Unsymmetrically Twisted Luminescent Zinc(II) Complex
2018Co-Authors: Tomohiro Hojo, Ryota Matsuoka, Tatsuya NabeshimaAbstract:A macrocyclic Dipyrrin tetramer containing flexible m-phenylene linkages and its tetranuclear zinc(II) complex were synthesized. The obtained complex has an unsymmetrical figure-of-eight structure because of the conformational flexibility of the macrocyclic framework. The first μ-hydroxo- and μ-acetato-bridged dinuclear zinc(II) Dipyrrin complex structure is realized in the twisted macrocyclic complex. Furthermore, the complex exhibited an efficient emission in toluene and chloroform
Mir Wais Hosseini - One of the best experts on this subject based on the ideXlab platform.
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strapping a benzaldehyde appended 2 2 bis Dipyrrin zn ii double stranded helicate using imine bond formation
Dalton Transactions, 2019Co-Authors: Fan Zhang, Stephane A Baudron, Audrey Fluck, Mir Wais HosseiniAbstract:A novel linear binuclear Zn(ii)/2,2'-bis-Dipyrrin double-stranded helicate bearing peripheral p-benzaldehyde moieties has been strapped by formation of imine bonds upon reaction with m-xylylenediamine and characterized by 1H- and 13C-NMR spectroscopy, UV-Visible spectroscopy and high-resolution mass spectrometry.
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ni ii Dipyrrin complexes bearing peripheral pyridyl or imidazolyl groups self assemble into 2 and 3 d coordination polymers
CrystEngComm, 2013Co-Authors: Antoine Beziau, Stephane A Baudron, Guillaume Rogez, Mir Wais HosseiniAbstract:While the numerous reported Ni(II) Dipyrrin complexes are discrete species, derivatives bearing peripheral pyridyl or imidazolyl groups self-assemble into coordination networks. As reported with Cd(II) salts, reaction of the Dipyrrin ligand functionalized with a 4-pyridyl moiety with Ni(OAc)2 affords a 2D coordination polymer in which the Ni(II) cation, in an octahedral environment, is bound to two Dipyrrinato chelates and two pyridyl groups, in cis arrangement, belonging to neighbouring complexes. In the crystal, the layers are homochiral with a consecutive ΔΛΔΛ stacking. Interestingly, analogous reaction with the derivative bearing a peripheral phenyl-4-pyridyl unit forms a similar 2D organization, yet expanded owing to the presence of the phenyl spacer. In this case, the formation of homochiral sheets is also observed, however with a single enantiomer of the complex in the crystal. Furthermore, whereas a distorted 2D coordination polymer is obtained with the novel Dipyrrin ligand appended with a phenyl-3-pyridyl group, a 3D coordination polymer is formed with the slightly more flexible derivative bearing an imidazolyl moiety.
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stepwise construction of grid type cu ii cd ii heterometallic mofs based on an imidazole appended Dipyrrin ligand
Chemical Communications, 2012Co-Authors: Antoine Beziau, Stephane A Baudron, Dmitry Pogozhev, Audrey Fluck, Mir Wais HosseiniAbstract:An imidazole-appended Dipyrrin ligand yields, upon coordination to Cu(II) cations, a linear metallatecton that self-assembles with Cd(II) salts to afford 2D grid-type MOFs which, upon parallel stacking, lead to porous crystals offering 1D channels.
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excited state properties and energy transfer within Dipyrrin based binuclear iridium platinum dyads the effect of ortho methylation on the spacer
Chemistry: A European Journal, 2012Co-Authors: Catherine Bronner, Mir Wais Hosseini, Cristian A Strassert, Aurelie Guenet, Luisa De Cola, Manoel Veiga, Stephane A BaudronAbstract:Luminescent cyclometalated iridium complexes based on pyridyl appended Dipyrrin ligands were prepared and characterized both in the solid state and in solution. The functionalization of the peripheral pyridyl moiety causes dramatic changes on the emission properties of both mono- and hetero- binuclear complexes. A detailed photophysical investigation of the two mononuclear derivatives of the [(Ppy)(2)Ir(dpm-py)] family (Ppy=2-phenylpyridine, dpm-py=5-(4-pyridyl)Dipyrrin) was carried out. Introduction of methyl groups at the 3 and 5 positions on the pyridyl unit diminishes the non-radiative rate constant by locking the peripheral pyridyl group orthogonally to the Dipyrrinato plane. Thus, they limit the rotational degree of freedom, as well as the charge-transfer character of the excited state. The coordination of these two complexes to a cyclometalated [(dppy)Pt] fragment (dppy=2,6-diphenylpyridine) led to the formation of binuclear species in which the iridium and platinum complexes behave as acceptors and donors, respectively. In these heterobinuclear compounds, the methyl groups do not influence the energy transfer efficiency, which is estimated to be above 90 %. However, they do limit the charge-transfer character of the acceptor's excited state, as well as its rotational degree of freedom, thus avoiding the detrimental effect upon the photophysical performance.
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Dipyrrin based silver 2 2 metallamacrocycles
Dalton Transactions, 2011Co-Authors: Dmitry Pogozhev, Stephane A Baudron, Mir Wais HosseiniAbstract:The synthesis and characterization of a series of [2 + 2] metallamacrocycles based on combinations of silver salts AgX (X = BF4−, PF6−, SbF6−, TfO−) with pyridyl, p-phenyl-pyridyl and p-phenyl-imidazolyl appended Dipyrrin (dpm) derivatives is reported. In these species, the silver ion is linearly coordinated to one of the two pyrrolic groups of the dpm moiety through the nitrogen atom and to a N atom belonging to the peripheral coordinating group. The organisation of the cyclic complexes in the solid state is dependent on the nature of the anion X− and on the hydrogen bonding patterns formed with the pyrrolic NH group, acting as a donor. Furthermore, in some cases, d10-d10 argentophilic interactions are observed between consecutive macrocyclic complexes in the crystalline phase. The robustness of some of the complexes obtained compounds was investigated by 1H- and 13C-NMR spectroscopy which revealed the structural integrity of the cyclic species in solution. A DOSY NMR study on the cyclic entity based on the imidazolyl appended dpm further assessed that the complex present in solution was indeed the [2 + 2] metallamacrocycle.
Stephane A Baudron - One of the best experts on this subject based on the ideXlab platform.
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Dipyrrin based metal complexes reactivity and catalysis
Dalton Transactions, 2020Co-Authors: Stephane A BaudronAbstract:Sometimes named half-porphyrins, bis-pyrrolic Dipyrrin ligands endow their metal complexes with unique properties such as the potential to functionalize the heterocyclic backbone or the meso position and the ability to catalyze interesting chemical transformations. Thus, strategies towards the derivatization of or at the meso group and the use of Dipyrrin metal complexes for the formation of a broad range of polypyrrolic derivatives such as 2,2'-bis-Dipyrrins, nor-/hetero-corroles and porphynoids have been elaborated. Furthermore, the chelating ability of Dipyrrins and the possibility of modifying their steric and electronic characteristics by functionalization can be exploited for the development of numerous complexes featuring appealing properties. Hence, C-H activation/amination, polymerization or oxidation reactions can be catalyzed by Dipyrrin metal complexes and classical reagents such as Grignard species, Rh-based or Suzuki-Miyaura catalysts have been revisited by incorporation of Dipyrrins in the coordination sphere of the metal cations. This contribution aims to review and illustrate all these aspects, highlighting the potential of these complexes for the design and synthesis of valuable organic compounds and metallo-organic architectures.
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strapping a benzaldehyde appended 2 2 bis Dipyrrin zn ii double stranded helicate using imine bond formation
Dalton Transactions, 2019Co-Authors: Fan Zhang, Stephane A Baudron, Audrey Fluck, Mir Wais HosseiniAbstract:A novel linear binuclear Zn(ii)/2,2'-bis-Dipyrrin double-stranded helicate bearing peripheral p-benzaldehyde moieties has been strapped by formation of imine bonds upon reaction with m-xylylenediamine and characterized by 1H- and 13C-NMR spectroscopy, UV-Visible spectroscopy and high-resolution mass spectrometry.
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luminescent Dipyrrin based metal complexes
ChemInform, 2013Co-Authors: Stephane A BaudronAbstract:While they may have been overshadowed by the brightness of their BODIPY analogues, Dipyrrin based metal complexes have recently appeared as novel interesting luminescent species owing to the development of various synthetic strategies for the preparation of such coordination compounds with appreciable quantum yields and tuneable emission wavelength. Not only the rigidification brought by functionalization of the Dipyrrin backbone either at position 5 or positions 1 and 9, but also a careful choice of the ligands present in the complex coordination sphere have been key in these developments leading to bright and stable emitters. At position 5, equivalent to the meso position of a porphyrin, introduction of peripheral groups, such as the mesityl moiety hindering the rotational freedom of this unit, has been particularly targeted, hence limiting a favourable non-radiative deactivation pathway. Regarding positions 1 and 9, their proximity to the metal center has prompted their use for the introduction of additional coordinating units, thus providing a pseudo-macrocyclic character to the ligands. In this perspective article, the different types of modification of Dipyrrin as well as the resulting metal complexes incorporating these derivatives, their photophysical properties and their applications in sensing and materials science are reviewed.
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ni ii Dipyrrin complexes bearing peripheral pyridyl or imidazolyl groups self assemble into 2 and 3 d coordination polymers
CrystEngComm, 2013Co-Authors: Antoine Beziau, Stephane A Baudron, Guillaume Rogez, Mir Wais HosseiniAbstract:While the numerous reported Ni(II) Dipyrrin complexes are discrete species, derivatives bearing peripheral pyridyl or imidazolyl groups self-assemble into coordination networks. As reported with Cd(II) salts, reaction of the Dipyrrin ligand functionalized with a 4-pyridyl moiety with Ni(OAc)2 affords a 2D coordination polymer in which the Ni(II) cation, in an octahedral environment, is bound to two Dipyrrinato chelates and two pyridyl groups, in cis arrangement, belonging to neighbouring complexes. In the crystal, the layers are homochiral with a consecutive ΔΛΔΛ stacking. Interestingly, analogous reaction with the derivative bearing a peripheral phenyl-4-pyridyl unit forms a similar 2D organization, yet expanded owing to the presence of the phenyl spacer. In this case, the formation of homochiral sheets is also observed, however with a single enantiomer of the complex in the crystal. Furthermore, whereas a distorted 2D coordination polymer is obtained with the novel Dipyrrin ligand appended with a phenyl-3-pyridyl group, a 3D coordination polymer is formed with the slightly more flexible derivative bearing an imidazolyl moiety.
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stepwise construction of grid type cu ii cd ii heterometallic mofs based on an imidazole appended Dipyrrin ligand
Chemical Communications, 2012Co-Authors: Antoine Beziau, Stephane A Baudron, Dmitry Pogozhev, Audrey Fluck, Mir Wais HosseiniAbstract:An imidazole-appended Dipyrrin ligand yields, upon coordination to Cu(II) cations, a linear metallatecton that self-assembles with Cd(II) salts to afford 2D grid-type MOFs which, upon parallel stacking, lead to porous crystals offering 1D channels.
Alison Thompson - One of the best experts on this subject based on the ideXlab platform.
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Asymmetric Dipyrrin and F‑BODIPYs Conjugated to Terminal Alkynes and Alkenes
2017Co-Authors: Carlotta Figliola, Katherine N. Robertson, Sarah Greening, Alison ThompsonAbstract:An asymmetric meso-H Dipyrrin featuring a conjugated terminal alkyne substituent was converted to its corresponding difluoro boron complex, and the extent of π-conjugation was extended using Sonogashira cross-coupling. Treatment of the alkyne-substituted Dipyrrin with BF3·OEt2 and NEt3 revealed the reactivity of the conjugated terminal alkyne toward Lewis-activated electrophilic substitution and led to the isolation of F-BODIPYs bearing terminal bromovinyl and enol substituents
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Asymmetric Dipyrrin and F-BODIPYs Conjugated to Terminal Alkynes and Alkenes
Journal of Organic Chemistry, 2017Co-Authors: Carlotta Figliola, Sarah Greening, Katherine Robertson, Alison ThompsonAbstract:An asymmetric meso-H Dipyrrin featuring a conjugated terminal alkyne substituent was converted to its corresponding difluoro boron complex, and the extent of π-conjugation was extended using Sonogashira cross-coupling. Treatment of the alkyne-substituted Dipyrrin with BF 3 ·OEt 2 and NEt 3 revealed the reactivity of the conjugated terminal alkyne toward Lewis-activated electrophilic substitution and led to the isolation of F-BODIPYs bearing terminal bromovinyl and enol substituents.
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Synthesis of symmetric meso-H Dipyrrin hydrobromides from 2-formyl pyrroles
Synlett, 2014Co-Authors: Kate-lyn A. R. Lund, Alison ThompsonAbstract:The reaction of 2-formylpyrroles in acidic methanol gives the corresponding symmetric, meso-H-4,6-Dipyrrin hydrobromides. This convenient strategy involves initial deformylation under the acidic conditions, followed by immediate in situ reaction of the resulting α-free pyrrole with the remaining 2-formylpyrrole in solution to give the Dipyrrin hydrobromide salt in good yield.
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synthesis and characterisation of the unsubstituted Dipyrrin and 4 4 dichloro 4 bora 3a 4a diaza s indacene improved synthesis and functionalisation of the simplest bodipy framework
Chemical Communications, 2013Co-Authors: Brandon R Groves, Travis Lundrigan, Sarah M Crawford, Cherif F Matta, Shahin Sowlatihashjin, Alison ThompsonAbstract:An improved and scalable synthesis of the unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene framework facilitates access to the previously unreported parent Dipyrrin HCl salt, as well as 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene.
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an improved method for the synthesis of f bodipys from Dipyrrins and bis Dipyrrin s
Organic Letters, 2012Co-Authors: Travis Lundrigan, Alexander E G Baker, Lauren E Longobardi, Tabitha E Wood, Deborah A Smithen, Sarah M Crawford, Stanley T Cameron, Alison ThompsonAbstract:An improved methodology for the synthesis of F-BODIPYs from Dipyrrins and bis(Dipyrrin)s is reported. This strategy employs lithium salts of Dipyrrins as intermediates that are then treated with only 1 equiv of boron trifluoride diethyletherate to obtain the corresponding F-BODIPYs. This scalable route to F-BODIPYs renders high yields with a facile purification process involving merely filtration of the reaction mixture through Celite in many cases.
Mangalampalli Ravikanth - One of the best experts on this subject based on the ideXlab platform.
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synthesis x ray structure spectral and electrochemical properties of a β meso covalently linked bodipy ru ii Dipyrrin complex
New Journal of Chemistry, 2014Co-Authors: Sheri Madhu, Sunit Kumar, Tamal Chatterjee, Mangalampalli RavikanthAbstract:We synthesized the BODIPY–Ru(II) Dipyrrin complex in decent yield by reacting β-dipyrromethanyl substituted BODIPY with [{(η6-C10H14)RuCl(μ-Cl)}2] under simple reaction conditions. The BODIPY–Ru(II) Dipyrrin complex was characterized by 1D, 2D, 13C, 11B, 19F NMR, HR-MS, UV-vis, fluorescence and electrochemical techniques. The BODIPY–Ru(II) Dipyrrin complex was further characterized by X-ray structure analysis, which showed that the Ru(II)-Dipyrrin complex is in perpendicular orientation to the BODIPY plane in the BODIPY–Ru(II) Dipyrrin complex. The ruthenium metal ion in the BODIPY–Ru(II) Dipyrrin complex is bonded to Dipyrrin nitrogens, one chloro group and arene ring (arene = C10H14) in an η6 manner resulting in a hexa coordination geometry around the Ru(II) ion. The absorption and steady-state fluorescence spectra of the BODIPY–Ru(II) Dipyrrin complex showed a broad and hypsochromically shifted absorption and emission bands compared to that of β-dipyrromethanyl substituted BODIPY. The electrochemical studies indicated that the BODIPY–Ru(II) Dipyrrin complex was easy to reduce compared to β-dipyrromethanyl substituted BODIPY supporting the electron deficient nature of the BODIPY–Ru(II) Dipyrrin complex.
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synthesis structure and spectral and electrochemical properties of 3 pyrrolyl bodipy metal Dipyrrin complexes
Dalton Transactions, 2014Co-Authors: Vellanki Lakshmi, Way Zen Lee, Mangalampalli RavikanthAbstract:The stable Dipyrrin substituted 3-pyrrolyl BODIPY (α-Dipyrrin 3-pyrrolyl BODIPY) was synthesized by oxidation of dipyrromethane substituted 3-pyrrolyl BODIPY with 2,3-dichloro-5,6-dicyano-benzoquinone in CH2Cl2 at room temperature. The α-Dipyrrin 3-pyrrolyl BODIPY is characterized by using HR-MS, 1D, 2D NMR and absorption spectroscopic techniques. The absorption spectrum of α-Dipyrrin 3-pyrrolyl BODIPY showed a characteristic absorption band at 630 nm and a charge transfer band at 717 nm due to intramolecular charge transfer from the Dipyrrin unit to the 3-pyrrolyl BODIPY unit. The 3-pyrrolyl BODIPY-metal Dipyrrin complexes (Pd(II), Re(I) and Ru(II)) were prepared by treating α-Dipyrrin 3-pyrrolyl BODIPY with appropriate metal salts in toluene–triethylamine at 100 °C and purified by silica gel column chromatography. The crystal structure obtained for the 3-pyrrolyl BODIPY-Pd(II) Dipyrrin complex showed that the 3-pyrrolyl BODIPY and metal Dipyrrin moieties are aligned to each other with an angle of 41.9°. The absorption studies showed a strong band at ∼620 nm corresponding to 3-pyrrolyl BODIPY moiety and a weak band at ∼530 nm corresponding to metal Dipyrrin unit with complete disappearance of the charge transfer band at 717 nm. The complexes are electron deficient and exhibited only reversible/quasi-reversible reductions in cyclic voltammetry.
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boron Dipyrrin porphyrin conjugates
Coordination Chemistry Reviews, 2013Co-Authors: Tamanna K Khan, Martin Broring, Sanjay Mathur, Mangalampalli RavikanthAbstract:Abstract Porphyrin/metalloporphyrin derivatives are a class of chromophores possessing favorable optical and redox properties for variety of applications ranging from materials to medicine. However, one drawback of porphyrin derivatives is their relatively poor absorption in the blue-green region of the spectrum (450–550 nm). One of the approaches for improving the absorption properties of porphyrin derivatives in blue-green region is their linking with chromophores that are capable of strongly absorbing in that region. Boron-Dipyrrins (BODIPYs) are highly fluorescent dyes which absorb strongly in blue-green region and possess complementary properties with porphyrins. In recent times, covalently and non-covalently linked BODIPY-porphyrin conjugates on their own and in association with other moieties such as fullerenes received lot of attention because of their use for various applications. Several synthetic strategies have been developed to synthesize simple BODIPY-porphyrin conjugates to complex photonic wires and gates. This review describes synthesis, properties and potential applications of covalently and non-covalently linked conjugates containing only BODIPY and porphyrin units as well as conjugates containing BODIPY, porphyrin and other groups such as fullerenes.
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photophysical properties of boron Dipyrrin appended porphyrins with heteroatom cores
Chemical Physics Letters, 2004Co-Authors: Duraisamy Kumaresan, Anindya Datta, Mangalampalli RavikanthAbstract:Abstract The photophysical properties of porphyrins with N 3 S and N 3 O cores appended with two boron-Dipyrrin units and porphyrins with N 2 S 2 and N 4 cores appended with four boron-Dipyrrin units are described. The steady-state fluorescence measurements indicate that the energy transfer from boron-Dipyrrin units to the porphyrin unit is efficient with N 4 and N 3 O porphyrin cores and less efficient with N 3 S and N 2 S 2 cores. The energy transfer rates calculated from lifetime measurements are also in support with these observations.
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synthesis of 21 thia and 21 oxaporphyrin building blocks and boron Dipyrrin appended systems
Tetrahedron, 2002Co-Authors: Duraisamy Kumaresan, Neeraj Agarwal, Iti Gupta, Mangalampalli RavikanthAbstract:Abstract A series of 21-thia and 21-oxaporphyrin building blocks bearing iodo-, ethynyl-and aldehyde functional groups were synthesized and characterized. These porphyrins are ideal building blocks for the construction of unsymmetrical porphyrin arrays containing two dissimilar porphyrin cores. The building blocks were used to construct boron–Dipyrrin appended core-modified porphyrin systems under mild palladium coupling conditions. A preliminary steady state fluorescence measurements suggested that boron–Dipyrrin unit transfers the energy to both 21-oxaporphyrin and 21-thiaporphyrin and the efficiency depends on the orientation of the boron–Dipyrrin units and the core structure of the porphyrin.