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

Research output

3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)11475-11484
Number of pages10
JournalChemistry - A European Journal
Volume24
Issue number44
DOIs
Publication statusPublished - 1 Jan 2018

Fingerprint

Halogens
Platinum
Pyridine
phosphine
Dimethyl Sulfoxide
Cyanides
Chromophores
Quantum efficiency
Hydrogen bonds
Derivatives
Crystals
pyridine

Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Sivchik, Vasily ; Sarker, Rajib Kumar ; Liu, Zong Ying ; Chung, Kun You ; Grachova, Elena V. ; Karttunen, Antti J. ; Chou, Pi Tai ; Koshevoy, Igor O. / Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 44. pp. 11475-11484.
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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",
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Sivchik, V, Sarker, RK, Liu, ZY, Chung, KY, Grachova, EV, Karttunen, AJ, Chou, PT & Koshevoy, IO 2018, 'Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts', Chemistry - A European Journal, vol. 24, no. 44, pp. 11475-11484. https://doi.org/10.1002/chem.201802182

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, Vol. 24, No. 44, 01.01.2018, p. 11475-11484.

Research output

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.

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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

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JO - Chemistry - A European Journal

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