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Volumn 15, Issue 11, 2009, Pages 2536-2547

"Helter-skelter-like" perylene polyisocyanopeptides

Author keywords

Electron transport; Perylene diimides; Polyisocyanides; Polymers

Indexed keywords

CHROMOPHORES; DYNAMICS; ELECTRON TRANSITIONS; ELECTRON TRANSPORT PROPERTIES; EXCITONS; HYDROGEN; HYDROGEN BONDS; MOLECULAR DYNAMICS; POLYMERS; SCAFFOLDS; SPECTROSCOPIC ANALYSIS; STEREOCHEMISTRY;

EID: 62349117551     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200801746     Document Type: Article
Times cited : (63)

References (80)
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    • After one week in tetrachloroethane solution no changes in the CD spectrum were observed, however, the fluorescence spectrum revealed a small monomer like signal (<1.5% monomer, which slowly became stronger in time. The monomer-like emission might be the result of the unwinding of the helix at its terminals or slow decomposition of the polymers at its terminals, because of reaction of the polyimide backbone with carbene- or radical-like species in solution. In the solid state the polymer is very stable over periods of up to 2 years. Differential scanning calorimetry (DSC) showed an endothermic peak at 850C in the heating trace with a corresponding exothermic peak at 58°C in the cooling trace, which can be attributed to the melting and crystallization of the alkyl tails in the periphery of the polymer, respectively, Figure S4
    • After one week in tetrachloroethane solution no changes in the CD spectrum were observed, however, the fluorescence spectrum revealed a small monomer like signal (<1.5% monomer), which slowly became stronger in time. The monomer-like emission might be the result of the unwinding of the helix at its terminals or slow decomposition of the polymers at its terminals, because of reaction of the polyimide backbone with carbene- or radical-like species in solution. In the solid state the polymer is very stable over periods of up to 2 years. Differential scanning calorimetry (DSC) showed an endothermic peak at 850C in the heating trace with a corresponding exothermic peak at 58°C in the cooling trace, which can be attributed to the melting and crystallization of the alkyl tails in the periphery of the polymer, respectively. (Figure S4).
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    • The calculations have been done in gas phase, hence the more collapsed conformation is also the most stable. Because solvent effects are not taken into account, we have not ruled out stable structures on the basis of the sole energetic argument. Absorption and CD spectra have been done for a number of conformera and the comparison to experiment allowed us to identity the most likely conformations in solution
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    • For each chain, the ground-state geometries of the individual chromophores were extracted from the full helical structures and single point INDO/CCSD calculations were performed on the H-adjusted molecules. The obtained vertical excitation energies and excitonic couplings (computed within the transition density approach) were then used to solve the Holstein Hamiltonian within the two-particle approximation.(see refs. [61,62])
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.