Linked Life Data

20209522

Source:http://linkedlifedata.com/resource/pubmed/id/20209522

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
12
pubmed:dateCreated
2010-3-24
pubmed:abstractText
Novel conglomerates consisting of saddle-distorted Sn(IV)(DPP) (H(2)DPP = dodecaphenylporphyrin) complexes and mu(3)-O-centered and carboxylato-bridged trinuclear Ru(III) clusters linked by pyridine carboxylates were synthesized and characterized. Sn(IV)-DPP complexes with Cl(-), OH(-), and 3- and 4-pyridine carboxylates ligands were characterized by spectroscopic methods and X-ray crystallography. Reactions of [Sn(DPP)(pyridinecarboxylato)(2)] with trinuclear Ru(III) clusters gave novel conglomerates in moderate yields. The conglomerates are stable in solution as demonstrated by (1)H NMR and electrospray ionization mass spectrometry (ESI-MS) measurements, which show consistent spectra with those expected from their structures, and also by electrochemical measurements, which exhibit reversible multistep redox processes. This stability stems from the saddle distortion of the DPP(2-) ligand to enhance the Lewis acidity of the Sn(IV) center that strengthens the axial coordination of the linker. The fast intramolecular photoinduced electron transfer from the Sn(IV)(DPP) unit to trinuclear Ru(III) clusters, affording the electron-transfer (ET) state {Sn(DPP(*+))-Ru(II)Ru(III)(2)}, was observed by femtosecond laser flash photolysis. The lifetimes of ET states of the conglomerates were determined to be in the range 98-446 ps, depending on the clusters and energies of the ET states. The reorganization energy of the electron transfer was determined to be 0.58+/-0.08 eV in light of the Marcus theory of electron transfer. The rate constants of both the photoinduced electron transfer and the back electron transfer in the conglomerates fall in the Marcus inverted region due to the small reorganization energy of electron transfer.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Mar
pubmed:issn
1521-3765
pubmed:author
pubmed:issnType
Electronic
pubmed:day
22
pubmed:volume
16
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
3646-55
pubmed:meshHeading
pubmed:year
2010
pubmed:articleTitle
Construction of Sn(IV) porphyrin/trinuclear ruthenium cluster dyads linked by pyridine carboxylates: photoinduced electron transfer in the Marcus inverted region.
pubmed:affiliation
Department of Material and Life Science, Graduate School of Engineering, Osaka University and SORST (JST), 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan. kojima@chem.tsukuba.ac.jp
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't