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Steric Engineering of Cyclometalated Pt(II) Complexes toward High-Contrast Monomer-Excimer-Based Mechanochromic and Vapochromic Luminescence. | LitMetric

Ligands play a crucial role in the supramolecular photoluminescence properties of Pt(II) square-planar complexes. To improve the luminescence color responses of N∧C∧N cyclometalated Pt(II) complexes to external stimuli such as mechanical stress and chemical vapors, we have conducted a steric engineering of the previous systems - [ , 56, 4978-4989] by introducing two -butyl groups to the tridentate ligand to form complexes -. Unlike the "too low" or "too high" steric hindrance of the NCNPt core in -, the combined steric effects of the -butyl groups at one side and the pentiptycene group at the other side of the NCNPt core in are "just right" for generating as-prepared powders with pure monomer (green) emission or pure excimer (red) emission, depending on the rate of precipitation from solutions. The synergistic steric effects are also beneficial to the solid-state luminescence quantum efficiency (30-36%). As a result of the differences in steric interactions and thus in the relative monomer vs excimer emission intensity, each complex of - performs a two-step luminescence mechanochromism and vapochromism with different color patterns. This work provides an intriguing example of steric engineering of Pt(II) complexes toward highly emissive molecular solids with high-contrast mechanochromic and vapochromic luminescence.

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http://dx.doi.org/10.1021/acs.inorgchem.0c01390DOI Listing

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