Carbene–Metal–Amide Polycrystalline Materials Feature Blue Shifted Energy yet Unchanged Kinetics of Emission

Jiale Feng; Elliot J. Taffet; Antti-Pekka M. Reponen; Alexander S. Romanov; Yoann Olivier; Vincent Lemaur; Lupeng Yang; Mikko Linnolahti; Manfred Bochmann; David Beljonne; Dan Credgington

doi:10.1021/acs.chemmater.0c01363

journal article·2020-06-09Open access

Carbene–Metal–Amide Polycrystalline Materials Feature Blue Shifted Energy yet Unchanged Kinetics of Emission

Jiale Feng, Elliot J. Taffet, Antti-Pekka M. Reponen, Alexander S. Romanov, Yoann Olivier, Vincent Lemaur, Lupeng Yang, Mikko Linnolahti, Manfred Bochmann, David Beljonne, Dan Credgington

Chemistry of Materials· Volume 32· Issue 11

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Source abstract

Abstract

The nature of carbene–metal–amide (CMA) photoluminescence in the solid state is explored through spectroscopic and quantum-chemical investigations on a representative Au-centered molecule. The crystalline phase offers well-defined coplanar geometries—enabling the link between molecular conformations and photophysical properties to be unravelled. We show that a combination of restricted torsional distortion and molecular electronic polarization blue shift the charge-transfer emission by around 400 meV in the crystalline versus the amorphous phase, through energetically raising the less-dipolar S1 state relative to S0. This blue shift brings the lowest charge-transfer states very close to the localized carbazole triplet state, whose structured emission is observable at low temperature in the polycrystalline phase. Moreover, we discover that the rate of intersystem crossing and emission kinetics are unaffected by the extent of torsional distortion. We conclude that more coplanar triplet equilibrium conformations control the photophysics of CMAs.

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Research context

OpenAlex topics: Organic Light-Emitting Diodes Research · Luminescence and Fluorescent Materials · Synthesis and Properties of Aromatic Compounds

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Cavendish Laboratory, Department of Physics, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, United Kingdom

Department of Chemistry, Stanford University, Stanford, California 94305, United States

School of Chemistry, University of East Anglia, Earlham Road, Norwich NR4 7TJ, United Kingdom

Unité de Chimie Physique Théorique et Structurale & Laboratoire de Physique du Solide, Namur Institute of Structured Matter, Université de Namur, Rue de Bruxelles, 61, 5000 Namur, Belgium

Laboratory for Chemistry of Novel Materials, University of Mons, Place du Parc 20, 7000 Mons, Belgium

Department of Chemistry, University of Eastern Finland, Joensuu Campus, FI-80101 Joensuu, Finland

Funding

Engineering and Physical Sciences Research Council · Royal Society · Belgian American Educational Foundation · Osk. Huttusen s??ti? · Academy of Finland · H2020 European Research Council · European Commission / R?gion Wallonne · Walloon Region · Consortium des ?quipements de Calcul Intensif

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