J-aggregation, its impact on excited state dynamics and unique solvent effects on macroscopic assembly of a core-substituted naphthalenediimide
KAUST DepartmentPhysical Sciences and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/553003
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AbstractHerein we reveal a straightforward supramolecular design for the H-bonding driven J-aggregation of an amine-substituted cNDI in aliphatic hydrocarbons. Transient absorption spectroscopy reveals sub-ps intramolecular electron transfer in isolated NDI molecules in a THF solution followed by a fast recombination process, while a remarkable extension of the excited state lifetime by more than one order of magnitude occurred in methylcyclohexane likely owing to an increased charge-separation as a result of better delocalization of the charge-separated states in J-aggregates. We also describe unique solvent-effects on the macroscopic structure and morphology. While J-aggregation with similar photophysical characteristics was noticed in all the tested aliphatic hydrocarbons, the morphology strongly depends on the “structure” of the solvents. In linear hydrocarbons (n-hexane, n-octane, n-decane or n-dodecane), formation of an entangled fibrillar network leads to macroscopic gelation while in cyclic hydrocarbons (methylcyclohexane or cyclohexane) although having a similar polarity, the cNDI exhibits nanoscale spherical particles. These unprecedented solvent effects were rationalized by establishing structure-dependent specific interactions of the solvent molecules with the cNDI which may serve as a general guideline for solvent-induced morphology-control of structurally related self-assembled materials.
CitationJ-aggregation, its impact on excited state dynamics and unique solvent effects on macroscopic assembly of a core-substituted naphthalenediimide 2015, 7 (15):6729 Nanoscale
PublisherRoyal Society of Chemistry (RSC)