Correlative Microscopy of Morphology and Luminescence of Cu porphyrin aggregates

TL;DR

This study investigates the relationship between morphology and luminescence in Cu porphyrin aggregates, revealing how structure influences fluorescence, phosphorescence, and molecular orientation, with implications for energy transfer in molecular assemblies.

Contribution

It provides the first spatially correlative analysis of morphology and luminescence in Cu porphyrin aggregates, linking internal order to emission properties and polarization behavior.

Findings

Phosphorescence is stronger than fluorescence and correlates with dye amount.

Strands show more fluorescence than isotropic islands, indicating fewer non-radiative channels.

Luminescence saturation is explained by attenuation and multireflection effects.

Abstract

Transfer of energy and information through molecule aggregates requires as one important building block anisotropic, cable-like structures. Knowledge on the spatial correlation of luminescence and morphology represents a prerequisite in the understanding of internal processes and will be important for architecting suitable landscapes. In this context we study the morphology, fluorescence and phosphorescence of molecule aggregate structures on surfaces in a spatially correlative way. We consider as two morphologies, lengthy strands and isotropic islands. It turns out that phosphorescence is quite strong compared to fluorescence and the spatial variation of the observed intensities is largely in line with the amount of dye. However in proportion, the strands exhibit more fluorescence than the isotropic islands suggesting weaker non-radiative channels. The ratio fluorescence to phosphorescence appears to be correlated with the degree of aggregation or internal order. The heights at which luminescence saturates is explained in the context of attenuation and emission multireflection, inside the dye. This is supported by correlative photoemission electron microscopy which is more sensitive to the surface region. The lengthy structures exhibit a pronounced polarization dependence of the luminescence with a relative dichroism up to about 60%, revealing substantial perpendicular orientation preference of the molecules with respect to the substrate and parallel with respect to the strands.