TY - JOUR

T1 - Diversifying the luminescence of phenanthro-diimine ligands in zinc complexes

AU - Temerova, Diana

AU - Kisel, Kristina S.

AU - Eskelinen, Toni

AU - Melnikov, Alexei S.

AU - Kinnunen, Niko

AU - Hirva, Pipsa

AU - Shakirova, Julia R.

AU - Tunik, Sergey P.

AU - Grachova, Elena V.

AU - Koshevoy, Igor O.

N1 - Publisher Copyright: © the Partner Organisations. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/5/21

Y1 - 2021/5/21

N2 - Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole (L1) is a facile block for the construction of multichromophore organic molecules, and simultaneously serves as a chelating diimine ligand. The coordination of L1 to zinc halides enhances the intraligand charge transfer and decreases the emission energy. For the iodide derivative, intra- and intermolecular heavy atom effects lead to a dual singlet-triplet emission with a temperature-dependent ratio of fluorescence and phosphorescence bands in the crystalline state. Decoration of the anthracene core with pyridyl-phenanthroimidazole units (L2 and L3) changes the localization of the lowest energy electronic transitions to the former polyaromatic motif. The solid-state photophysical characteristics of L2 and L3-based compounds strongly depend on the intermolecular interactions between the constituting p-systems (phenanthrene and anthracene), which are perturbed by the ZnX2 coordinated fragments. Modulation of p-stacking contacts in these molecular materials containing L2 and L3 chromophores forms a basis for dynamic optical properties, responsive to mechanical, thermal, or chemical stimuli.

AB - Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole (L1) is a facile block for the construction of multichromophore organic molecules, and simultaneously serves as a chelating diimine ligand. The coordination of L1 to zinc halides enhances the intraligand charge transfer and decreases the emission energy. For the iodide derivative, intra- and intermolecular heavy atom effects lead to a dual singlet-triplet emission with a temperature-dependent ratio of fluorescence and phosphorescence bands in the crystalline state. Decoration of the anthracene core with pyridyl-phenanthroimidazole units (L2 and L3) changes the localization of the lowest energy electronic transitions to the former polyaromatic motif. The solid-state photophysical characteristics of L2 and L3-based compounds strongly depend on the intermolecular interactions between the constituting p-systems (phenanthrene and anthracene), which are perturbed by the ZnX2 coordinated fragments. Modulation of p-stacking contacts in these molecular materials containing L2 and L3 chromophores forms a basis for dynamic optical properties, responsive to mechanical, thermal, or chemical stimuli.

KW - ROOM-TEMPERATURE PHOSPHORESCENCE

KW - COORDINATION POLYMERS

KW - SOLID-STATE

KW - FLUORESCENT PROPERTIES

KW - OPTICAL-PROPERTIES

KW - EXCIMER EMISSION

KW - SCHIFF-BASE

KW - ANTHRACENE

KW - ZN(II)

KW - BLUE

UR - http://www.scopus.com/inward/record.url?scp=85106150339&partnerID=8YFLogxK

U2 - 10.1039/d1qi00149c

DO - 10.1039/d1qi00149c

M3 - Article

AN - SCOPUS:85106150339

VL - 8

SP - 2549

EP - 2560

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 10

ER -