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Porphyrin Dyads (porphyrin + dyad)

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Chemistry100%

Selected Abstracts

Synthesis of Triazole-Bridged Unsymmetrical Porphyrin Dyads and Porphyrin,Ferrocene Conjugates

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2010
Vijayendra S. Shetti
Abstract A simple method has been used to synthesize four porphyrin azides with cores such as N4, N3S, N2SO and N2S2 in 60,90,% yields by treating the corresponding aminoporphyrins with tert -butyl nitrite (tBuONO) and azidotrimethylsilane (TMSN3) in THF/CH3CN under mild reaction conditions. The hitherto unknown aminoporphyrins with heteroatom cores were synthesized from their corresponding nitroporphyrins by standard SnCl2/HCl reduction. The azidoporphyrins were used to synthesize six triazole-bridged unsymmetrical porphyrin dyads containing two different types of porphyrin sub-units as well as five triazole-bridged porphyrin,ferrocene conjugates under CuI -catalyzed "click" reaction conditions. Various CuI -catalyzed reaction conditions were studied and the best yields of triazole-bridged dyads and conjugates were obtained with CuI/DIPEA in THF/CH3CN at room temperature for overnight. The unsymmetrical porphyrin dyads and porphyrin,ferrocene conjugates were characterized by various spectroscopic and electrochemical techniques. In unsymmetrical porphyrin dyads, the NMR, absorption and electrochemical studies indicate a weak interaction between the two porphyrin sub-units. However, preliminary photophysical studies support an efficient singlet-singlet energy transfer from one porphyrin unit to another in five unsymmetrical dyads reported here. In porphyrin,ferrocene conjugates, the fluorescence of porphyrin was quenched significantly due to photo-induced electron transfer from ferrocene to porphyrin. [source]

ChemInform Abstract: Parallel (Face-to-Face) versus Perpendicular (Edge-to-Face) Alignment of Electron Donors and Acceptors in Fullerene Porphyrin Dyads: The Importance of Orientation in Electron Transfer.

CHEMINFORM, Issue 3 2002
Dirk M. Guldi
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Single-Step Electron Transfer on the Nanometer Scale: Ultra-Fast Charge Shift in Strongly Coupled Zinc Porphyrin,Gold Porphyrin Dyads

CHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2008
Jérôme Fortage Dr.
Abstract The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II),gold(III) bisporphyrin dyads (ZnPSAuP+) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert -(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45,Å. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state .+ZnPSAuP., whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2,ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (,=2.3,ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnPAuP+ dyads linked via meso -phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical impact of the attachment position of the spacer on the porphyrin on the electron transfer rate, and this strategy can represent a useful approach to develop molecular photonic devices for long-range charge separations. [source]

Synthesis of Triazole-Bridged Unsymmetrical Porphyrin Dyads and Porphyrin,Ferrocene Conjugates

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2010
Vijayendra S. Shetti
Abstract A simple method has been used to synthesize four porphyrin azides with cores such as N4, N3S, N2SO and N2S2 in 60,90,% yields by treating the corresponding aminoporphyrins with tert -butyl nitrite (tBuONO) and azidotrimethylsilane (TMSN3) in THF/CH3CN under mild reaction conditions. The hitherto unknown aminoporphyrins with heteroatom cores were synthesized from their corresponding nitroporphyrins by standard SnCl2/HCl reduction. The azidoporphyrins were used to synthesize six triazole-bridged unsymmetrical porphyrin dyads containing two different types of porphyrin sub-units as well as five triazole-bridged porphyrin,ferrocene conjugates under CuI -catalyzed "click" reaction conditions. Various CuI -catalyzed reaction conditions were studied and the best yields of triazole-bridged dyads and conjugates were obtained with CuI/DIPEA in THF/CH3CN at room temperature for overnight. The unsymmetrical porphyrin dyads and porphyrin,ferrocene conjugates were characterized by various spectroscopic and electrochemical techniques. In unsymmetrical porphyrin dyads, the NMR, absorption and electrochemical studies indicate a weak interaction between the two porphyrin sub-units. However, preliminary photophysical studies support an efficient singlet-singlet energy transfer from one porphyrin unit to another in five unsymmetrical dyads reported here. In porphyrin,ferrocene conjugates, the fluorescence of porphyrin was quenched significantly due to photo-induced electron transfer from ferrocene to porphyrin. [source]

Nonlinear Optical Properties of Ferrocene- and Porphyrin,[60]Fullerene Dyads

CHEMPHYSCHEM, Issue 7 2007
Evangelia Xenogiannopoulou Dr.
Abstract A series of novel [60]fullerene,ferrocene and [60]fullerene,porphyrin dyads, in which a fullerene and an electron donating moiety are attached through a flexible triethylene glycol linker are synthesized and their nonlinear optical (NLO) response studied. Specifically, the third-order susceptibility ,(3) of all fullerene derivatives are measured in toluene solutions by the optical Kerr effect (OKE) technique using 532 nm, 35 ps laser pulses and their second hyperpolarizability , are determined. All fullerene dyads studied exhibit enhancement of their NLO response compared to pristine fullerenes which has been attributed to the formation of a charge separated state. All experimentally measured hyperpolarizability , values are also calculated by the semiempirical methods AM1 and PM3. A good correlation is found between the theoretical and experimental values, suggesting that simple semiempirical methods can be employed for the designing and optimization of the fullerene-containing dyads displaying improved nonlinear responses. [source]