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

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 language	English
Pages (from-to)	4743-4753
Number of pages	11
Journal	Chemistry of Materials
Volume	32
Issue number	11
DOIs	https://doi.org/10.1021/acs.chemmater.0c01363
Publication status	Published - 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.

Funders	Funder 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 - FNRS	2.5020.11
Engineering and Physical Sciences Research Council	EP/L015978/1
European Research Council	338944, URF\R1\180288, RGF\EA\181008
Walloon Region	n1117545
Royal Society	RGF\EA\180041, UF130278

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10.1021/acs.chemmater.0c01363

2020_OlivierY_articleAccepted author manuscript, 1.31 MB

Cite this

@article{fe60f58e46de4633b2f74c26803cb843,

title = "Carbene-Metal-Amide Polycrystalline Materials Feature Blue Shifted Energy yet Unchanged Kinetics of Emission",

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.",

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

note = "Funding Information: The authors thank Prof. Anna K{\"o}hler and Prof. Heinz B{\"a}ssler 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/R{\'e}gion Wallonne (FEDER – BIORGEL project), the Consortium des {\'E}quipements de Calcul Intensif (C{\'E}CI), 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 F{\'e}d{\'e}ration Wallonie-Bruxelles, infrastructure funded by the Walloon Region under Grant Agreement n1117545 and FRS-FNRS. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jun,

day = "9",

doi = "10.1021/acs.chemmater.0c01363",

language = "English",

volume = "32",

pages = "4743--4753",

journal = "Chemistry of Materials",

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number = "11",

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T1 - Carbene-Metal-Amide Polycrystalline Materials Feature Blue Shifted Energy yet Unchanged Kinetics of Emission

AU - Feng, Jiale

AU - Taffet, Elliot J.

AU - Reponen, Antti Pekka M.

AU - Romanov, Alexander S.

AU - Olivier, Yoann

AU - Lemaur, Vincent

AU - Yang, Lupeng

AU - Linnolahti, Mikko

AU - Bochmann, Manfred

AU - Beljonne, David

AU - Credgington, Dan

N1 - Funding Information: The authors thank Prof. Anna Köhler and Prof. Heinz Bässler 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/Région Wallonne (FEDER – BIORGEL project), the Consortium des Équipements de Calcul Intensif (CÉCI), 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 Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under Grant Agreement n1117545 and FRS-FNRS. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/6/9

Y1 - 2020/6/9

N2 - 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.

AB - 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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U2 - 10.1021/acs.chemmater.0c01363

DO - 10.1021/acs.chemmater.0c01363

M3 - Article

AN - SCOPUS:85088652081

SN - 0897-4756

VL - 32

SP - 4743

EP - 4753

JO - Chemistry of Materials

JF - Chemistry of Materials

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ER -

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

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

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