Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts

Vasily Sivchik; Rajib Kumar Sarker; Zong Ying Liu; Kun You Chung; Elena V. Grachova; Antti J. Karttunen; Pi Tai Chou; Igor O. Koshevoy

doi:10.1002/chem.201802182

Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts

Vasily Sivchik, Rajib Kumar Sarker, Zong Ying Liu, Kun You Chung, Elena V. Grachova, Antti J. Karttunen^*, Pi Tai Chou, Igor O. Koshevoy

^*Corresponding author for this work

Department of Chemistry and Materials Science

Research output: Contribution to journal › Article › Scientific › peer-review

Abstract

Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh₃/Cl (b), PPh₃/CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC₆F₅ and I₂C₆F₄). Compounds 1a and 2a (L/Y=DMSO/Cl) afford the adducts 1aI₂C₆F₄ and 2aI₂C₆F₄, which feature IS_btpy/Iπ_btpy and IO_DMSO/ICl short contacts, respectively. The phosphane-cyanide derivatives 1c and 2c (L/Y=PPh₃/CN) co-crystallise with both IC₆F₅ and I₂C₆F₄. None of the phpy-based species 3a-3c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φ_em=0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T₁→S₀ transition by providing a rigid environment around the chromophore.

Original language	English
Pages (from-to)	11475 –11484
Number of pages	10
Journal	Chemistry - A European Journal
DOIs	https://doi.org/10.1002/chem.201802182
Publication status	Published - 3 Jul 2018
MoE publication type	A1 Journal article-refereed

Keywords

Crystal engineering
Halogens
Luminescence
Noncovalent interactions
Platinum

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@article{58f920c88e3f409c8e2d50a83b49545e,

title = "Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts",

abstract = "Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh3/Cl (b), PPh3/CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC6F5 and I2C6F4). Compounds 1a and 2a (L/Y=DMSO/Cl) afford the adducts 1aI2C6F4 and 2aI2C6F4, which feature ISbtpy/Iπbtpy and IODMSO/ICl short contacts, respectively. The phosphane-cyanide derivatives 1c and 2c (L/Y=PPh3/CN) co-crystallise with both IC6F5 and I2C6F4. None of the phpy-based species 3a-3c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φem=0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T1→S0 transition by providing a rigid environment around the chromophore.",

keywords = "Crystal engineering, Halogens, Luminescence, Noncovalent interactions, Platinum",

author = "Vasily Sivchik and Sarker, {Rajib Kumar} and Liu, {Zong Ying} and Chung, {Kun You} and Grachova, {Elena V.} and Karttunen, {Antti J.} and Chou, {Pi Tai} and Koshevoy, {Igor O.}",

year = "2018",

month = jul,

day = "3",

doi = "10.1002/chem.201802182",

language = "English",

pages = "11475 –11484",

journal = "CHEMISTRY: A EUROPEAN JOURNAL",

issn = "0947-6539",

}

Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts. / Sivchik, Vasily; Sarker, Rajib Kumar; Liu, Zong Ying; Chung, Kun You; Grachova, Elena V.; Karttunen, Antti J.; Chou, Pi Tai; Koshevoy, Igor O.

In: Chemistry - A European Journal, 03.07.2018, p. 11475 –11484.

Research output: Contribution to journal › Article › Scientific › peer-review

TY - JOUR

T1 - Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts

AU - Sivchik, Vasily

AU - Sarker, Rajib Kumar

AU - Liu, Zong Ying

AU - Chung, Kun You

AU - Grachova, Elena V.

AU - Karttunen, Antti J.

AU - Chou, Pi Tai

AU - Koshevoy, Igor O.

PY - 2018/7/3

Y1 - 2018/7/3

N2 - Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh3/Cl (b), PPh3/CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC6F5 and I2C6F4). Compounds 1a and 2a (L/Y=DMSO/Cl) afford the adducts 1aI2C6F4 and 2aI2C6F4, which feature ISbtpy/Iπbtpy and IODMSO/ICl short contacts, respectively. The phosphane-cyanide derivatives 1c and 2c (L/Y=PPh3/CN) co-crystallise with both IC6F5 and I2C6F4. None of the phpy-based species 3a-3c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φem=0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T1→S0 transition by providing a rigid environment around the chromophore.

AB - Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh3/Cl (b), PPh3/CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC6F5 and I2C6F4). Compounds 1a and 2a (L/Y=DMSO/Cl) afford the adducts 1aI2C6F4 and 2aI2C6F4, which feature ISbtpy/Iπbtpy and IODMSO/ICl short contacts, respectively. The phosphane-cyanide derivatives 1c and 2c (L/Y=PPh3/CN) co-crystallise with both IC6F5 and I2C6F4. None of the phpy-based species 3a-3c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φem=0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T1→S0 transition by providing a rigid environment around the chromophore.

KW - Crystal engineering

KW - Halogens

KW - Luminescence

KW - Noncovalent interactions

KW - Platinum

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U2 - 10.1002/chem.201802182

DO - 10.1002/chem.201802182

M3 - Article

SP - 11475

EP - 11484

JO - CHEMISTRY: A EUROPEAN JOURNAL

JF - CHEMISTRY: A EUROPEAN JOURNAL

SN - 0947-6539

ER -