Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers

Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers Full article

Journal

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Output data

Year: 2016, Volume: 45, Number: 2, Pages: 515-524 Pages count : 10 DOI: 10.1039/c5dt04005a

Authors

Vinogradova Katerina A. ^1,2 , Krivopalov Viktor P. ³ , Nikolaenkova Elena B. ³ , Pervukhina Natalia V. ¹ , Naumov Dmitrii Yu. ^1,2 , Boguslavsky Evgenii G. ¹ , Bushuev Mark B. ^1,2

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, Nikolaev Inst Inorgan Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

Two pyrimidine-based ligands, 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(morpholino)pyrimidine (L-2) and 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-phenoxypyrimidine (L-3), and a series of mixed-valence copper(I,II)halide complexes, [Cu(L-2)(2)Br](2)[Cu2Br4] (1), [Cu(L-2)(2)Cl][CuCl2] (2), and [(Cu2LBr3)-Br-3](n) (3), have been synthesized. The complex [Cu(L-2)(2)Br](2)[Cu2Br4] was prepared by the reaction of L-2 with CuBr2 in a 1 : 1 molar ratio in MeCN. Its chlorido-analogue, the complex [Cu(L-2)(2)Cl][CuCl2], was synthesized by the reaction between L-2, CuCl2 and CuCl in a 2 : 1 : 1 molar ratio in MeCN. The ligand L-2 acts as a chelating one. In the structures of the complexes [Cu(L-2)(2)Br](2)[Cu2Br4] and [Cu(L-2)(2)Cl][CuCl2] the Cu2+ ion is in the cationic part of the complex whereas the Cu+ ion is located in the anionic part. The best way to synthesize the mixed-valence 1D coordination polymer [(Cu2LBr3)-Br-3] n is to react CuBr2 with L-3 in a 2 : 1 molar ratio in the MeCN/CHCl3 mixture on heating. In the structure of [(Cu2LBr3)-Br-3] n the ligand L-3 shows chelating/bridging tridentate coordination. This is the first example of the tridentate coordination of 4-(1H-pyrazol-1-yl)-6-R-pyrimidines. The striking difference between the coordination behavior of L-2 and L-3 (chelating bidentate vs. chelating/bridging coordination) is related with the possibility of rotation of the 6-phenoxy group around the C-O bond which makes the N1 pyrimidine atom less sterically hindered, enabling it to participate in metal ion binding. Importantly, all copper ions in [(Cu2LBr3)-Br-3] n show similar tetrahedral environments, CuNBr3 and CuN2Br2, which is extremely rare for mixed-valence copper(I, II) compounds. The ligands L-2 and L-3 show blue emission which is quenched upon their coordination to copper ions. The 1D coordination polymer [(Cu2LBr3)-Br-3] n shows high thermal stability and unusual solvent-occlusion properties. The role of the substituents favoring the formation of the mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines is discussed.

Vinogradova K.A. , Krivopalov V.P. , Nikolaenkova E.B. , Pervukhina N.V. , Naumov D.Y. , Boguslavsky E.G. , Bushuev M.B.
Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers
Dalton Transactions. 2016. V.45. N2. P.515-524. DOI: 10.1039/c5dt04005a WOS Scopus РИНЦ

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