TY - JOUR
T1 - Organic room-temperature phosphorescence from halogen-bonded organic frameworks
T2 - hidden electronic effects in rigidified chromophores
AU - Zhou, Jiawang
AU - Stojanović, Ljiljana
AU - Berezin, Andrey A.
AU - Battisti, Tommaso
AU - Gill, Abigail
AU - Kariuki, Benson M.
AU - Bonifazi, Davide
AU - Crespo-Otero, Rachel
AU - Wasielewski, Michael R.
AU - Wu, Yi-Lin
N1 - Funding Information:
D. B. gratefully acknowledges the EU through the MSCA-ITN-ETN (GA No. 722591 – project PHOTOTRAIN) and School of Chemistry at Cardiff University for generous nancial support. R. C.-O. acknowledges funding from the EPSRC (EP/R029385/1) and Leverhulme Trust (RPG-2019-122). This research utilised Queen Mary's Apocrita HPC facility. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0020168 (M. R. W.). The authors thank Professor Kenneth D. M. Harris and Dr Colan E. Hughes (Cardiff) for the help with powder X-ray diffraction.
Funding Information:
D. B. gratefully acknowledges the EU through the MSCA-ITN-ETN (GA No. 722591 - project PHOTOTRAIN) and School of Chemistry at Cardiff University for generous financial support. R. C.-O. acknowledges funding from the EPSRC (EP/R029385/1) and Leverhulme Trust (RPG-2019-122). This research utilised Queen Mary's Apocrita HPC facility. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0020168 (M. R. W.). The authors thank Professor Kenneth D. M. Harris and Dr Colan E. Hughes (Cardiff) for the help with powder X-ray diffraction.
Publisher Copyright:
© 2021 The Royal Society of Chemistry.
PY - 2021/1/14
Y1 - 2021/1/14
N2 - Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control. This journal is
AB - Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control. This journal is
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U2 - 10.1039/d0sc04646a
DO - 10.1039/d0sc04646a
M3 - Article
C2 - 34163810
AN - SCOPUS:85099722918
VL - 12
SP - 767
EP - 773
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 2
ER -