Efficient Synthesis of Porphyrin-Containing, Benzoquinone-Terminated, Rigid Polyphenylene Dendrimers

• Published in: Journal of organic chemistry 2003-01, Vol.68 (2), p.247-261
• Main Authors: Capitosti, Gregory J, Guerrero, Carol D, Binkley, David E, Rajesh, Cheruvallil S, Modarelli, David A
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Organic chemistry; Preparations and properties
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo026520p

A series of rigid polyphenylene, free-base porphyrin-containing dendrimers terminated with either dimethoxybenzene or benzoquinone end-groups were prepared by a combined divergent and convergent synthesis. Unlike previous routes for preparing polyphenylene dendrimers that are incompatible with end-groups bearing certain functional moieties, the synthetic methodology chosen for this work enables incorporation of functional groups on the dendrimer end-groups during preparation of the dendrimer wedges and during synthesis of the final dendrimer. The basic strategy utilized a convergent preparation of dendrimer wedges using Suzuki coupling conditions, which were then either attached to a porphyrin core in a divergent coupling step or cyclized to form the porphyrin dendrimer in a convergent step. The latter approach was found to be more general and resulted in higher yields and more readily separated products. Steady-state absorption measurements for these dendrimers showed Soret and Q-band absorptions typical of free-base porphyrins. Preliminary steady-state fluorescence measurements of these dendrimers indicate quenching of the S1 state of the free-base porphyrin in all benzoquinone-containing dendrimers that is attributed to efficient electron-transfer from the excited porphyrin to the benzoquinone end-groups. The amount of fluorescence quenching was in good agreement with the number of benzoquinone groups at the dendrimer periphery and the distance between the porphyrin and benzoquinone groups as calculated by semiempirical (AM1) molecular orbital calculations.