TY - JOUR

T1 - Intermolecular interactions-photophysical properties relationships in phenanthrene-9,10-dicarbonitrile assemblies

AU - Afanasenko, Anastasiia M.

AU - Novikov, Alexander S.

AU - Chulkova, Tatiana G.

AU - Grigoriev, Yakov M.

AU - Kolesnikov, Ilya E.

AU - Selivanov, Stanislav I.

AU - Starova, Galina L.

AU - Zolotarev, Andrey A.

AU - Vereshchagin, Anatoly N.

AU - Elinson, Michail N.

N1 - Funding Information: This work has been supported by Russian Foundation for Basic Research (project 16-33-60063 ). We thank the Centre for Optical and Laser Materials Research, Research Centre for X-ray Diffraction Studies, Educational Resource Centre of Chemistry, Centre for Chemical Analysis and Materials Research, and Centre of Magnetic Resonance (all belong to Saint Petersburg State University) for physicochemical measurements.

PY - 2020/1/5

Y1 - 2020/1/5

N2 - Phenanthrene-9,10-dicarbonitriles show various luminescence behaviour in solution and in the solid state. Aggregation patterns of phenanthrene-9,10-dicarbonitriles govern their luminescent properties in the solid state. Single crystal structures of phenanthrene-9,10-dicarbonitriles showed head-to-tail intraplane (or quasi-intraplane) intermolecular interactions and π-stacking patterns with eclipsing of molecules when viewed orthogonal to the stacking plane. The π-stacking interactions were detected in the X-ray structures of phenanthrene-9,10-dicarbonitriles and studied by DFT calculations at the M06–2X/6–311++G(d,p) level of theory and topological analysis of the electron density distribution within the framework of QTAIM method. The estimated strength of the C⋯C contacts responsible for the π-stacking interactions is 0.6–1.1 kcal/mol. The orientation of molecules in crystals depends on the substituents in phenanthrene-9,10-dicarbonitriles. Distinct molecular orientation and packing arrangements in crystalline phenanthrene-9,10-dicarbonitriles ensured perturbed electronic communication among the nearest and non-nearest molecules through an interplay of excimer and dipole couplings. As a result, the intermolecular interactions govern the solid state luminescence of molecules.

AB - Phenanthrene-9,10-dicarbonitriles show various luminescence behaviour in solution and in the solid state. Aggregation patterns of phenanthrene-9,10-dicarbonitriles govern their luminescent properties in the solid state. Single crystal structures of phenanthrene-9,10-dicarbonitriles showed head-to-tail intraplane (or quasi-intraplane) intermolecular interactions and π-stacking patterns with eclipsing of molecules when viewed orthogonal to the stacking plane. The π-stacking interactions were detected in the X-ray structures of phenanthrene-9,10-dicarbonitriles and studied by DFT calculations at the M06–2X/6–311++G(d,p) level of theory and topological analysis of the electron density distribution within the framework of QTAIM method. The estimated strength of the C⋯C contacts responsible for the π-stacking interactions is 0.6–1.1 kcal/mol. The orientation of molecules in crystals depends on the substituents in phenanthrene-9,10-dicarbonitriles. Distinct molecular orientation and packing arrangements in crystalline phenanthrene-9,10-dicarbonitriles ensured perturbed electronic communication among the nearest and non-nearest molecules through an interplay of excimer and dipole couplings. As a result, the intermolecular interactions govern the solid state luminescence of molecules.

KW - Phenanthrene-9,10-dicarbonitriles

KW - DFT studies

KW - Fluorescence

KW - pi-Stacking

UR - http://www.scopus.com/inward/record.url?scp=85071720178&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2019.07.036

DO - 10.1016/j.molstruc.2019.07.036

M3 - Article

VL - 1199

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

M1 - 126789

ER -