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

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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.

Original languageEnglish
Pages (from-to)4743-4753
Number of pages11
JournalChemistry of Materials
Volume32
Issue number11
DOIs
Publication statusPublished - 9 Jun 2020

Funding

The authors thank Prof. Anna Ko\u0308hler and Prof. Heinz Ba\u0308ssler for fruitful discussions. J.F. acknowledges his parents for Ph.D financial support. E.J.T. acknowledges support from the Belgian American Educational Foundation. D.C. acknowledges support from the Royal Society (Grant No. UF130278). A.-P.M.R. acknowledges support from the Royal Society (Grant No. RGF\\EA\\180041) and the Osk, Huttunen fund. M.B. acknowledges the ERC Advanced Investigator Award (Grant No. 338944-GOCAT). A.S.R. acknowledges support from the Royal Society (Grant No. URF\\R1\\180288 and RGF\\EA\\181008). This work was supported by the EPSRC Cambridge NanoDTC, EP/L015978/1. M.L. acknowledges the Academy of Finland Flagship Programme, Photonics Research and Innovation (PREIN), decision 320166. (TD)DFT computations were made possible by use of the Finnish Grid and Cloud Infrastructure resources (urn:nbn:fi:research-infras-2016072533). Research in Mons is supported by FNRS-FRFC and Consortium des Equipements de Calcul Intensif (CECI). D.B. is the FNRS research director. The work in Mons was supported by the European Commission/Re\u0301gion Wallonne (FEDER \u2013 BIORGEL project), the Consortium des E\u0301quipements de Calcul Intensif (CE\u0301CI), funded by the Fonds National de la Recherche Scientifique (F.R.S.-FNRS) under Grant No. 2.5020.11 as well as the Tier-1 supercomputer of the Fe\u0301de\u0301ration Wallonie-Bruxelles, infrastructure funded by the Walloon Region under Grant Agreement n1117545 and FRS-FNRS.

FundersFunder number
FNRS‐FRFC
European Commission/Région Wallonne
Consortium des Equipements de Calcul Intensif
Belgian American Educational Foundation
European Commission
Fédération Wallonie-Bruxelles
European Regional Development Fund
Fonds De La Recherche Scientifique - FNRS2.5020.11
Engineering and Physical Sciences Research CouncilEP/L015978/1
European Research Council338944, URF\R1\180288, RGF\EA\181008
Walloon Regionn1117545
Royal SocietyRGF\EA\180041, UF130278

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