Efficient Near-Infrared Luminescence of Self-Assembled Platinum(II) Complexes: From Fundamentals to Applications

Conspectus Designing bright and efficient near-infrared (NIR) emitters has drawn much attention due to numerous applications ranging from biological imaging, medical therapy, optical communication, and night-vision devices. However, polyatomic organic and organometallic molecules with energy gaps close to the deep red and NIR regime are subject to dominant nonradiative internal conversion (IC) processes, which drastically reduces the emission intensity and exciton diffusion length of organic materials and hence hampers the optoelectronic performances. To suppress nonradiative IC rates, we suggested two complementary approaches to solve the issues: exciton delocalization and molecular deuteration. First, exciton delocalization efficiently suppresses the molecular reorganization energy through partitioning to all aggregated molecules. According to the IC theory together with the effect of exciton delocalization, the simulated nonradiative rates with the energy gap ΔE = 104 cm–1 decrease by around 104 fold when the exciton delocalization length equals 5 (promoting vibronic frequency ω l = 1500 cm–1). Second, molecular deuterations reduce Franck–Condon vibrational overlaps and vibrational frequencies of promoting modes, which decreases IC rates by 1 order of magnitude in comparison to the rates of nondeuterated molecules under ΔE of 104 cm–1. Although deuteration of molecules has long been attempted to increase emission intensity, the results have been mixed. Here, we provide a robust derivation of the IC theory to demonstrate its validity, especially to emission in the NIR region. The concepts are experimentally verified by the strategic design and synthesis of a class of square-planar Pt­(II) complexes, which form crystalline aggregates in vapor deposited thin films. The packing geometries are well characterized by the grazing angle X-ray diffraction (GIXD), showing domino-like packing arrangements with the short ππ separation of 3.4–3.7 Å. Upon photoexcitation, such closely packed assemblies exhibit intense NIR emission maximized in the 740–970 nm region through metal–metal-to-ligand charge transfer (MMLCT) transition with unprecedented photoluminescent quantum yield (PLQY) of 8–82%. To validate the existence of exciton delocalization, we applied time-resolved step-scan Fourier transform UV–vis spectroscopy to probe the exciton delocalization length of Pt­(II) aggregates, which is 5–9 molecules (2.1–4.5 nm) assuming that excitons mainly delocalized along th