TY - JOUR

T1 - Solid State Phosphorescence Enhancement of PtII-Based Emitters Via Combination of π-Hole(Isocyano Group)⋅⋅⋅ dz2[PtII] and I···Cl Halogen-Bonding Interactions

AU - Katkova, Svetlana A.

AU - Antonova, Elina V.

AU - Cheranyova, Anna M.

AU - Ivanov, Daniil M.

AU - Kinzhalov, Mikhail A.

PY - 2023/10/13

Y1 - 2023/10/13

N2 - The PtII isocyanide complex [Pt(ppy)Cl(CNC6H4-C≡C-Ph)] (1, Hppy=2-phenylpyridine) was co-crystallized with 1,4-diiodotetrafluorobenzene (1,4-DITFB), yielding 1·½(1,4-DITFB) adduct. The I···Cl halogen-bonding and π-π-stacking interactions combined with the rare π-hole(isocyano group)⋅⋅⋅dz2[PtII] interactions were identified via analysis of X-ray diffraction data of the co-crystals. These two types of structure-determining interactions supplemented each other, and the system of I⋯Cl and π-hole(isocyano group)⋅⋅⋅dz2[PtII] contacts achieved a 1D extended ladder-type architecture. The density functional theory calculations, employing a set of computational tools, verified the role of I⋯Cl and π-hole(isocyano group)⋅⋅⋅dz2[PtII] noncovalent bonds in the spectrum of noncovalent forces. The solid-state photophysical study revealed an amplification of luminescence intensity in the co-crystals, which is attributed to the suppression of the nonradiative relaxation pathways due to an increase in the rigidity of the chromophore center.

AB - The PtII isocyanide complex [Pt(ppy)Cl(CNC6H4-C≡C-Ph)] (1, Hppy=2-phenylpyridine) was co-crystallized with 1,4-diiodotetrafluorobenzene (1,4-DITFB), yielding 1·½(1,4-DITFB) adduct. The I···Cl halogen-bonding and π-π-stacking interactions combined with the rare π-hole(isocyano group)⋅⋅⋅dz2[PtII] interactions were identified via analysis of X-ray diffraction data of the co-crystals. These two types of structure-determining interactions supplemented each other, and the system of I⋯Cl and π-hole(isocyano group)⋅⋅⋅dz2[PtII] contacts achieved a 1D extended ladder-type architecture. The density functional theory calculations, employing a set of computational tools, verified the role of I⋯Cl and π-hole(isocyano group)⋅⋅⋅dz2[PtII] noncovalent bonds in the spectrum of noncovalent forces. The solid-state photophysical study revealed an amplification of luminescence intensity in the co-crystals, which is attributed to the suppression of the nonradiative relaxation pathways due to an increase in the rigidity of the chromophore center.

KW - halogen bonding

KW - isocyanide ligands

KW - luminescence

KW - noncovalent interactions

KW - platinum(II) complexes

KW - π-hole interactions

UR - https://www.mendeley.com/catalogue/7ba9ae28-2fdb-35d4-bb61-2c9b1e371e27/

U2 - 10.3390/inorganics11100403

DO - 10.3390/inorganics11100403

M3 - Article

VL - 11

JO - Inorganics

JF - Inorganics

SN - 2304-6740

IS - 10

M1 - 403

ER -