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Volumn 60, Issue 38, 2004, Pages 8497-8508

Tripodal Ru(II) complexes with conjugated and non-conjugated rigid-rod bridges for semiconductor nanoparticles sensitization

Author keywords

ruthenium complexes; Sensitization; Titanium dioxide; Tripods

Indexed keywords

4 ETHYNYLPHENYLENE; ADAMANTANE DERIVATIVE; BENZENE DERIVATIVE; NANOPARTICLE; PHENANTHROLINE DERIVATIVE; RUTHENIUM COMPLEX; TITANIUM DIOXIDE; UNCLASSIFIED DRUG;

EID: 4444277618     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2004.06.124     Document Type: Article
Times cited : (23)

References (64)
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    • note
    • 2-2,2-bipyridine; Ad-Tripod=1,3,5-tris(p- carboxyphenyl)-7-adamantyl. The Ad-tripod notation is different from that used in our previous publications. In this paper the phenyl group in position 7 is considered part of the bridge.
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    • note
    • 2-bound Ru complexes, including the tripods
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    • ρLUMO=0.02)
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    • The use of an ethynyl bridge carrying the chromophore in Route A is not advantageous because it leads to a mixture, and is not feasible with chromophores that are incompatible with the organolithium reagents used in the carboxylation step.
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    • 1-Bis(ethynyl)-bicyclo[2.2.2]octane, with or without trialkylsilyl protecting groups, has been prepared by others, see for instance: Honegger, E.; Heilbronner, E.; Heß, N.; Martin, H. -D. Chem. Ber. 1987, 120, 187 and Ref. 18. We prepared it in two steps from bicyclo[2.2.2]octane-1,4- dicarboxyaldehyde (Kumar, K.; Wang, S. S.; Sukenik, C. N. J. Org. Chem. 1984, 49, 665) following the method reported for the synthesis of 1,4- bis(trimethylsilylethynyl)-cubane and 1,4-bis(ethynyl)-cubane from cubane-1,4-dicarboxyaldehyde (Eaton, P. E.; Galoppini, E.; Gilardi, R. J. Am. Chem. Soc. 1994, 116, 7588).
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    • 1-Bis(ethynyl)-bicyclo[2.2.2]octane, with or without trialkylsilyl protecting groups, has been prepared by others, see for instance: Honegger, E.; Heilbronner, E.; Heß, N.; Martin, H. -D. Chem. Ber. 1987, 120, 187 and Ref. 18. We prepared it in two steps from bicyclo[2.2.2]octane-1,4- dicarboxyaldehyde (Kumar, K.; Wang, S. S.; Sukenik, C. N. J. Org. Chem. 1984, 49, 665) following the method reported for the synthesis of 1,4- bis(trimethylsilylethynyl)-cubane and 1,4-bis(ethynyl)-cubane from cubane-1,4-dicarboxyaldehyde (Eaton, P. E.; Galoppini, E.; Gilardi, R. J. Am. Chem. Soc. 1994, 116, 7588).
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    • note
    • Tetrasubstituted products were not observed or found in trace amounts in this step
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    • note
    • 1H NMR of the mixture (see Supplementary data), (ii) the observation that 14 does not react in the cross coupling step, (iii) the observation that the polarity on silica is identical to that of 13, similar to what we have experienced when a H is replaced by a I group in tetraphenylmethane derivatives. Unreacted 14 was separated from the product after the cross-coupling, but could never be isolated in pure form


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