Chiral zinc(II) and cadmium(II) complexes with a dihydrophenanthroline ligand bearing (-)-alpha-pinene fragments: Synthesis, crystal structures and photophysical properties

Chiral zinc(II) and cadmium(II) complexes with a dihydrophenanthroline ligand bearing (-)-alpha-pinene fragments: Synthesis, crystal structures and photophysical properties Full article

Journal

Polyhedron
ISSN: 0277-5387

Output data

Year: 2016, Volume: 117, Pages: 437-444 Pages count : DOI: 10.1016/j.poly.2016.06.018

Tags

Chiral complexes; Pentacyclic heterocycle; Crystal structure; DFT-calculation; Photoluminescence

Authors

Kokina Tatyana E. ^1,2 , Glinskaya Ludmila A. ¹ , Tkachev Alexey V. ^2,3 , Plyusnin Victor F. ^2,4 , Tsoy Yuliya V. ² , Bagryanskaya Irina Yu. ^2,3 , Vasilyev Evgene S. ³ , Piryazev Dmitriy A. ^1,2 , Sheludyakova Liliya A. ^1,2 , Larionov Stanislav V. ^1,2

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, Nikolaev Inst Inorgan Chem, 3 Acad Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, 2 Pirogov Str, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Vorozhtsov Novosibirsk Inst Organ Chem, Siberian Branch, 9 Acad Lavrentiev Ave, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, Siberian Branch, 3 Inst Skaya, Novosibirsk 630090, Russia

Mononuclear and dinuclear zinc(II) and cadmium(II) complexes, [ZnLCl2] (1) and [Cd2L2Cl4] (2), with a chiral pentacyclic dihydrophenanthroline ligand L bearing a natural monoterpene (-)-alpha-pinene fragment were synthesized. DFT calculations of the specific rotation [alpha] and an NMR study show that the molecules of ligand L, complex 1 and the monomeric form of complex 2 exist in CDCl3 solutions with the P-helix conformation for the dihydrophenanthroline moiety. The dihydrophenanthroline fragments of L and mononuclear complex 1 also exists as a P-helix in the solid state, whereas the crystalline dinuclear complex 2 exists as an asymmetric dimer, [(Cd2Cl4LLM)-L-P], where L-P and L-M are the ligand with P-helix and M-helix conformations of the dihydrophenanthroline fragment respectively. Full sets of photophysical parameters for L and complexes 1 and 2 have been determined. Compounds L, 1 and 2 display blue luminescence (lambda(max) = 427, 405 and 415 nm in the solid state, respectively). The ligand L and complex 2 show moderate-to high quantum yields of 44% and 24%, respectively. The quantum yield for complex 1 is 6%. The emission lifetimes increase on going along the spectrum of luminescence, and in the deep red region, a rise of luminescence with times of 200500 ps is observed. These processes can be explained by the migration of excitons and the capture of excitation by "defective" centers. (C) 2016 Elsevier Ltd. All rights reserved.

Kokina T.E. , Glinskaya L.A. , Tkachev A.V. , Plyusnin V.F. , Tsoy Y.V. , Bagryanskaya I.Y. , Vasilyev E.S. , Piryazev D.A. , Sheludyakova L.A. , Larionov S.V.
Chiral zinc(II) and cadmium(II) complexes with a dihydrophenanthroline ligand bearing (-)-alpha-pinene fragments: Synthesis, crystal structures and photophysical properties
Polyhedron. 2016. V.117. P.437-444. DOI: 10.1016/j.poly.2016.06.018 WOS Scopus РИНЦ

Published print:

Oct 1, 2016

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