مشخصات پژوهش

صفحه نخست /Supramolecular structures of ...
عنوان Supramolecular structures of NiII and CuII with the sterically demanding Schiff base dyes driven by cooperative action of preagostic and other non-covalent interactions
نوع پژوهش مقاله چاپ‌شده در مجلات علمی
کلیدواژه‌ها extensive experimental and theoretical investigations on lphotophysical, structura
چکیده This work reports on synthesis and extensive experimental and theoretical investigations on photophysical, structural and thermal properties of the NiII and CuII discrete mononuclear homoleptic complexes [Ni(LI,II)2] and [Cu(LI,II)2] fabricated from the Schiff base dyes o-HOC6H4—CH=N—cyclo-C6H11 (HLI) and o-HOC10H6—CH=N—cyclo-C6H11 (HLII), containing the sterically crowding cyclo­hexyl units. The six-membered metallocycles adopt a clearly defined envelope conformation in [Ni(LII)2], while they are much more planar in the structures of [Ni(LI)2] and [Cu(LI,II)2]. It has been demonstrated by in-depth bonding analyses based on the ETS-NOCV and Interacting Quantum Atoms energy-decomposition schemes that application of the bulky substituents, containing several C—H groups, has led to the formation of a set of classical and unintuitive intra- and inter-molecular interactions. All together they are responsible for the high stability of [Ni(LI,II)2] and [Cu(LI,II)2]. More specifically, London dispersion dominated intramolecular C—H⋯O, C—H⋯N and C—H⋯H—C hydrogen bonds are recognized and, importantly, the attractive, chiefly the Coulomb driven, preagostic (not repulsive anagostic) C—H⋯Ni/Cu interactions have been discovered despite their relatively long distances (∼2.8–3.1 Å). All the complexes are further stabilized by the extremely efficient intermolecular C—H⋯π(benzene) and C—H⋯π(chelate) interactions, where both the charge-delocalization and London dispersion constituents appear to be crucial for the crystal packing of the obtained complexes. All the complexes were found to be photoluminescent in CH2Cl2, with [Cu(LII)2] exhibiting the most pronounced emission – the time-dependent density-functional-theory computations revealed that it is mostly caused by metal-to-ligand charge-transfer transitions.
پژوهشگران دمیر سفین (نفر ششم به بعد)، مایکل بولت (نفر ششم به بعد)، ماریا باباشینکا (نفر ششم به بعد)، قدرت محمودی (نفر ششم به بعد)، فلیپ ساگان (نفر پنجم)، مرسیدز کوکولکا (نفر چهارم)، مارسیز میتوراج (نفر سوم)، تاتیانا بورخانوا (نفر دوم)، آلکسی شرایو (نفر اول)