Naphthalene diimide derivatives

Fig. 8.14 Hydrogen bonded nanotube formed from a naphthalene diimide derivative, a The strucmre of the naphthalene diimide. b Hydrogen bonding pattern for the formation of the helical nanombe. c Crystal structure of the nanotube. Reprinted with permission from Ref. [58]. Copyright 2007, Wiley-VCH Verlag Gmbh and Co. KGaA, Weinheim...

Oxidative repair is not a unique feature of our Rh(III) complexes. We also demonstrated efficient long-range repair using a covalently tethered naphthalene diimide intercalator (li /0 1.9 V vs NHE) [151]. An intercalated ethidium derivative was ineffective at dimer repair, consistent with the fact that the reduction potential of Et is significantly below the potential of the dimer. Thymine dimer repair by a series of anthraquinone derivatives was also evaluated [151]. Despite the fact that the excited triplets are of sufficient potential to oxidize the thymine dimer ( 3 -/0 1.9 V vs NHE), the anthraquinone derivatives were unable to effect repair [152]. We attribute the lack of repair by these anthraquinone derivatives to their particularly short-lived singlet states anthraquinone derivatives that do not rapidly interconvert to the excited triplet state are indeed effective at thymine dimer repair [151]. These observations suggest that interaction of the dimer with the singlet state may be essential for repair. 

Scheme 8 Naphthalene diimide (18), pyrazinonaphthalimide (19), and bis pyrazino-naphthalimide derivatives (20, 21).

Table 14.1 presents a selection of donor/acceptor combinations that have shown notable solar cell efficiencies. Power conversion efficiencies of 1.5-2.2% have been demonstrated for a number of systems, with most blends utilizing either a CN-PPV derivative or the fluorene-dithienylbenzothiadiazole copolymer F8TBT as the acceptor. Despite their high electron mobilities, perylene diimide- and naphthalene diimide-based acceptors have shown disappointing efficiencies, though with optimization Zhou et al. have recently been able to achieve a power conversion efficiency of 2.2% with a perylene diimide acceptor [25]. 

Perylene and perinone pigments are closely related chemically and are manufaemred by essentially the same route. Perylenes are diimide derivatives of perylene-3,4,9,10-tetracarboxylic acid, while perinones are derivatives of naphthalene-1,4,5,8-tetracarboxylic acid (Herbst and Hunger, 1997). 

The benzo-derivative 16 is accessible through 1,4-dimethylnaphthalene, which on singlet oxygenation leads to the thermally labile naphthalene-1,4-endoperoxide. This endoperoxide expels singlet oxygen at ca. 10 °C, but diimide reduction below 0 °C in MeOH affords the stable dihydro derivative 16 (Eq. 11). 

Perylene pigments include the dianhydride and diimide of perylene tetracarboxylic acid along with derivatives of the diimide while perinone pigments are derived from naphthalene tetracarboxylic acid. 

Chen. G. Lean. J.T. Alcala. M. Mallouk, T.E. Modular synthesis of ir-acceptor cyclophanes derived from 1,4,5,8-naphthalenetetracarboxylic diimide and 1.5-dinitro-naphthalene. J. Org. Chem. 2001. 66. 3027-3034. 

Ketene formation using l,8-bis(dimethylamino)naphthalene 406 in the presence of benzoylqijinidine (BQd) as a known nucleophilic chiral catalyst and Zn(OXf)2 as Lewis acid catalyst and ori/io-benzoquinone diimides 407 as coreactants afforded quinoxaline derivatives 408 with high stereoselectivity nearly in all cases (Scheme 127) (2006JA13370). Ketene enolates 405 are suggested as the reaction intermediates. Transformation of the product 408 (R = Et) to 409 by reduction was also performed. 

Attractive interactions between electronically complementary aromatic tt-systems have been widely exploited in supramolecular chemistry since the first reports of their potential in this field some 30 years ago. More recently, work by Colquhoun, Hayes, and coworkers has demonstrated that such interactions can also be exploited in the design of healable polymer blends, whereby electron-rich pyrenyl end-groups intercalate into designed chain-folds in polyimides derived from naphthalene-1,4,5,8-tetra-carboxylic dianhydride. Initial computational and spectroscopic studies on model compounds showed that a chain-fold comprising two diimide units linked by a triethylenedioxy chain provided the ideal geometry for... 

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