π-Hole···dz2[PtII] Interactions with Electron-Deficient Arenes Enhance the Phosphorescence of PtII-Based Luminophores

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π-Hole···dz2[PtII] Interactions with Electron-Deficient Arenes Enhance the Phosphorescence of PtII-Based Luminophores. / Рожков, Антон Викторович; Ананьев, Иван; Gomila, Rosa; Frontera, Antonio; Кукушкин, Вадим Юрьевич.

In: Inorganic Chemistry, Vol. 59, No. 13, 06.07.2020, p. 9308–9314.

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

BibTeX

@article{aabd748d75a442e6a6e2e2850b127fe8,

title = "π-Hole···dz2[PtII] Interactions with Electron-Deficient Arenes Enhance the Phosphorescence of PtII-Based Luminophores",

abstract = "Two phosphorescent PtII-based cyclometalated complexes were co-crystallized with perfluorinated arenes to give 1:1 co-crystals. The X-ray study revealed that each of the complexes is embraced by arenesF to give infinite reverse sandwich structures. In four out of six structures, a dz2 orbital of PtII is directed to the arenesF ring via π-hole···dz2[PtII] interactions, whereas in the other two structures, the filled dz2 orbital is directed toward the arene C atoms. Computed molecular electrostatic potential surfaces of the arenesF and the complexes, noncovalent interaction indexes for the co-crystals, and natural bond orbital calculations indicate that π-hole···dz2[PtII] contacts (and, generally, the stacking) are of electrostatic origin. The solid-state photophysical study revealed up to 3.5-fold luminescence quantum yield and 15-fold lifetime enhancements in the co-crystals. This increase is associated with the strength of the π-hole···dz2[PtII] contact that is dependent on the π-acidity of the areneF and its spatial characteristics.",

keywords = "COMPLEXES, DESIGN, PI, LUMINESCENCE, COCRYSTALS",

author = "Рожков, {Антон Викторович} and Иван Ананьев and Rosa Gomila and Antonio Frontera and Кукушкин, {Вадим Юрьевич}",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jul,

day = "6",

doi = "10.1021/acs.inorgchem.0c01170",

language = "English",

volume = "59",

pages = "9308–9314",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

RIS

TY - JOUR

T1 - π-Hole···dz2[PtII] Interactions with Electron-Deficient Arenes Enhance the Phosphorescence of PtII-Based Luminophores

AU - Рожков, Антон Викторович

AU - Ананьев, Иван

AU - Gomila, Rosa

AU - Frontera, Antonio

AU - Кукушкин, Вадим Юрьевич

PY - 2020/7/6

Y1 - 2020/7/6

N2 - Two phosphorescent PtII-based cyclometalated complexes were co-crystallized with perfluorinated arenes to give 1:1 co-crystals. The X-ray study revealed that each of the complexes is embraced by arenesF to give infinite reverse sandwich structures. In four out of six structures, a dz2 orbital of PtII is directed to the arenesF ring via π-hole···dz2[PtII] interactions, whereas in the other two structures, the filled dz2 orbital is directed toward the arene C atoms. Computed molecular electrostatic potential surfaces of the arenesF and the complexes, noncovalent interaction indexes for the co-crystals, and natural bond orbital calculations indicate that π-hole···dz2[PtII] contacts (and, generally, the stacking) are of electrostatic origin. The solid-state photophysical study revealed up to 3.5-fold luminescence quantum yield and 15-fold lifetime enhancements in the co-crystals. This increase is associated with the strength of the π-hole···dz2[PtII] contact that is dependent on the π-acidity of the areneF and its spatial characteristics.

AB - Two phosphorescent PtII-based cyclometalated complexes were co-crystallized with perfluorinated arenes to give 1:1 co-crystals. The X-ray study revealed that each of the complexes is embraced by arenesF to give infinite reverse sandwich structures. In four out of six structures, a dz2 orbital of PtII is directed to the arenesF ring via π-hole···dz2[PtII] interactions, whereas in the other two structures, the filled dz2 orbital is directed toward the arene C atoms. Computed molecular electrostatic potential surfaces of the arenesF and the complexes, noncovalent interaction indexes for the co-crystals, and natural bond orbital calculations indicate that π-hole···dz2[PtII] contacts (and, generally, the stacking) are of electrostatic origin. The solid-state photophysical study revealed up to 3.5-fold luminescence quantum yield and 15-fold lifetime enhancements in the co-crystals. This increase is associated with the strength of the π-hole···dz2[PtII] contact that is dependent on the π-acidity of the areneF and its spatial characteristics.

KW - COMPLEXES

KW - DESIGN

KW - PI

KW - LUMINESCENCE

KW - COCRYSTALS

UR - http://www.scopus.com/inward/record.url?scp=85087531363&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/afd16104-79ef-3431-b885-5f218707ee9f/

U2 - 10.1021/acs.inorgchem.0c01170

DO - 10.1021/acs.inorgchem.0c01170

M3 - Article

VL - 59

SP - 9308

EP - 9314

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 13

ER -

ID: 60621488