Stabilization through p-dimethylaminobenzaldehyde of a new NLO-active phase of [E-4-(4-dimethylaminostyryl)-1-methylpyridinium] iodide : synthesis, structural characterization and theoretical investigation of its electronic properties
Articolo
Data di Pubblicazione:
2010
Citazione:
Stabilization through p-dimethylaminobenzaldehyde of a new NLO-active phase of [E-4-(4-dimethylaminostyryl)-1-methylpyridinium] iodide : synthesis, structural characterization and theoretical investigation of its electronic properties / F. Nunzi, S. Fantacci, E. Cariati, E. Tordin, N.P. Casati, P. Macchi. - In: JOURNAL OF MATERIALS CHEMISTRY. - ISSN 0959-9428. - 20:36(2010), pp. 7652-7660. [10.1039/c0jm00466a]
Abstract:
Co-crystallization of p-N(CH3)(2)C6H4CHO and E-4-(4-dimethylaminostyryl)-1-methylpyridinium iodide ([DAMS]I) gives a new solid state form (A), characterized by high non-linear-optical (NLO) activity and quite different from the well known [DAMS]I salt (centrosymmetric and therefore inactive). The X-ray structural characterization, although affected by the extended disorder of p-N(CH3)(2)C6H4CHO, addresses a new kind of aggregation for the [DAMS(+)] chromophore molecules. In fact, together with the often encountered J-type aggregation, an unprecedented "fishbone'' coupling is observed. Calculations using time-dependent density functional theory (TDDFT) prove that the absence of a J-aggregation band in the electronic absorption spectrum is due to the additional intermolecular interaction that quenches the expected J-type signal. Correlation between supramolecular arrangements of the chromophores and NLO properties is also discussed.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
2ND-order optical nonlinearities ; density-functional theory ; spatially separated systems ; transfer excited-states ; 2ND-harmonic generation ; molecular assemblies ; absorption-spectra; chromophores ; design ; crystal
Elenco autori:
F. Nunzi, S. Fantacci, E. Cariati, E. Tordin, N.P. Casati, P. Macchi
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