A New Class of Functionalized Terpyridyl Ligands as Building Blocks for Photosensitized Supramolecular Architectures. Synthesis, Structural, and Electronic Characterizations
- 26 January 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (7) , 1364-1377
- https://doi.org/10.1021/ja011069p
Abstract
A new class of triarylpyridinio-derivatized [4‘-(p-phenyl)n]terpyridyl ligands, R12R2TP+-(p)ntpy, was designed as a novel category of electron-acceptor (A)-substituted proto-photosensitizing molecules. The first elements of this versatile family of ligands (i.e., n = 0, 1 and R1 = R2 = H), H3TP+-tpy and H3TP+-ptpy, were synthesized as well as their Ru(II) and Os(II) complexes to form the related acceptor-functionalized M(tpy)22+ and M(ptpy)22+ photosensitizer components denoted P0 and P1, respectively. Within the P1 series of compounds, an electron-donor (D)-substituted ligand, Me2N-ptpy, was also involved and associated with H3TP+-ptpy, giving rise to various combinations (up to 10 polyad systems). The two resulting series of nanometer-scale rigid rod-like photosensitized supramolecular architectures are of potential interest for long-range photoinduced electron transfer purposes. The main structural features of such supermolecules were determined by comparing the results obtained from (i) single-crystal X-ray analysis of the two free ligands together with that of the P0A/Ru and P1A 2 /Ru complexes and (ii) a detailed solution 1H NMR study of the P0 series and, more specifically, of the P0A/Ru dyad (ROESY experiment). It is shown that the pseudoperpendicular conformation of the covalently linked A and P subunits found in the solid state is persistent in fluid medium; i.e., A is not conjugated with P (P0 and P1). The first insights regarding the consequences upon intercomponent couplings of combined substituent effects and conjugation (case of D-based polyads)or absence of conjugationare discussed in the light of ground-state electronic properties of the compounds.Keywords
This publication has 41 references indexed in Scilit:
- Reducible Nanosize MacrocyclesJournal of the American Chemical Society, 1999
- Convergent Synthesis of Betaine-30, a Solvatochromic Dye: An Advanced Undergraduate Project and DemonstrationJournal of Chemical Education, 1996
- Mixed-valent interactions in rigid dinuclear systems: electrochemical and spectroscopic studies of CrICr0 ions with controlled torsion of the biphenyl bridgeInorganic Chemistry, 1994
- Crystal structure of 1,2,4,6-tetraphenylpyridinium tetrabromoferrate(III)Journal of Chemical Crystallography, 1993
- Twisted internal charge transfer (TICT) effect in bis(4-cyanophenyl)piperazine, a pseudo-dimer of dimethylaminobenzonitrile: a comparative studyJournal of Photochemistry and Photobiology A: Chemistry, 1993
- Photoinduced electron transfer in supramolecular systems for artificial photosynthesisChemical Reviews, 1992
- Crystal structures of potassium cryptated salts of the diselenotelluride(2-), pyramidal TeSe32-, and mixed compounds containing pyramidal TeSe32- and chain TexSe4-x2- anions and selenium-77 and tellurium-125 solution NMR studies of the pyramidal selenothiotellurite anions TeSmSe3-m2- (m = 0 - 3)Inorganic Chemistry, 1991
- The development of versions 3 and 4 of the Cambridge Structural Database SystemJournal of Chemical Information and Computer Sciences, 1991
- Facile addition of small molecules to the osmium carbonyl sulfido cluster Os4(CO)12(.mu.3-S). Syntheses and crystal and molecular structures of Os4(CO)12(NHMe2)(.mu.3-S) and Os4(CO)12(.mu.-H)2(.mu.3-S)Inorganic Chemistry, 1986
- The Palladium‐Catalyzed Cross‐Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)]Angewandte Chemie International Edition in English, 1986