Creating hierarchical molecular block heterostructures, with the control over size, shape, optical, and electronic properties of each nanostructured building block can help develop functional applications, such as information storage, nanowire spectrometry, and photonic computing. However, achieving precise control over the position of molecular assemblies, and the dynamics of excitons in each block, remains a challenge. In the present work, the first fabrication of molecular heterostructures with the control of exciton dynamics in each block, is demonstrated. Additionally, these heterostructures are printable and can be precisely positioned using Direct Ink Writing-based (DIW) 3D printing technique, resulting in programable patterns. Singlet excitons with emission lifetimes on nanosecond or microsecond timescales and triplet excitons with emission lifetimes on millisecond timescales appear simultaneously in different building blocks, with an efficient energy transfer process in the heterojunction. These organic materials also exhibit stimuli-responsive emission by changing the power or wavelength of the excitation laser. Potential applications of these organic heterostructures in integrated photonics, where the versatility of fluorescence, phosphorescence, efficient energy transfer, printability, and stimulus sensitivity co-exist in a single nanowire, are foreseen.
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