Influence of the steric properties of pyridine ligands on the structure of complexes containing the {LnCd 2 (bzo) 7 } fr
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Russian Chemical Bulletin, International Edition, Vol. 69, No. 8, pp. 1544—1560, August, 2020
Influence of the steric properties of pyridine ligands on the structure of complexes containing the {LnCd2(bzo)7} fragment* M. A. Shmelev,а Yu. K. Voronina,a N. V. Gogoleva,a A. A. Sidorov,a M. A. Kiskin,a F. M. Dolgushin,b Yu. V. Nelyubina,b G. G. Aleksandrov,a† E. A. Varaksina,b,c I. V. Taydakov,b,c,d and I. L. Eremenkoa aN.
S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow, Russian Federation. Fax: +7 (495) 954 1279. E-mail: [email protected] bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation. Fax: +7 (499) 135 5085. E-mail: [email protected] cP. N. Lebedev Physical Institute, Russian Academy of Sciences, 53 Leninsky prosp., 119333 Moscow, Russian Federation. Fax: +7 (499) 135 7880. E-mail: [email protected] dMoscow Institute of Physics and Technology, 9 Institutskiy per., 141700 Dolgoprudny, Moscow region, Russian Federation. Fax: +7 (495) 408 4254. E-mail: [email protected] The reaction of Cd(NO3)2•4H2O and Eu(NO3)3•6H2O or Tb(NO3)3•6H2O with potassium 3,5-di-tert-butylbenzoate (Kbzo) and N-donor ligands (1,10-phenanthroline (phen), 2,4-lutidine (2,4-lut), 3,4-lutidine (3,4-lut), phenanthridine (phtd), 2,3-cyclododecenopyridine (cdpy), acridine (acr)) afforded heterometallic LnCd2 complexes: [EuCd2(bzo)7(EtOH)2(phen)] (2), [LnCd2(bzo)7(2,4-lut)4] (Ln = Eu (3), Tb (4)), [EuCd2(bzo)7(H2O)2(2,4-lut)2]•MeCN (5), [EuCd2(NO3)(bzo)6(EtOH)2(2,4-lut)2] (6), [EuCd2(bzo)7(H2O)(EtOH)(3,4-lut)2]•5EtOH (7), 3[EuCd2(bzo)7(H2O)2(phtd)2]•4phtd (8), [EuCd2(bzo)7(EtOH)3(cdpy)] (9), 2[EuCd2(bzo)2(EtOH)4]•acr (10). The structures of complexes 2, 3, and 5—10 were determined by single-crystal X-ray diffraction. The isostructurality of complexes 3 and 4 was confirmed by powder X-ray diffraction. The structure of the trinuclear {Ln2Cd} metal core is stable and independent of the type of peripheral ligands coordinated to cadmium atoms. Photoluminescent properties of compounds 3 and 4 were studied. Key words: cadmium, lanthanides, 3,5-di-tert-butylbenzoic acid, luminescence, X-ray diffraction.
Variations of geometric parameters of ligands involved in the heterometallic chain structural units {M2Xn(O2CR)k} (M = CoII, NiII, CuII, ZnII, CdII; X = Li (n = 2, k = 6), Mg (n = 1, k = 6), Ca (n = 1, k = 6), Ln (n = 1, 2, k = 7, 10)), in which 3d metals or cadmium are combined with lithium, magnesium, calcium, or lanthanide atoms,1—12 can be employed to get knowledge on conformational flexibility of these metal cores. These data are useful for the analysis of the structures of more complex polynuclear compounds, particularly metal-organic frameworks based on related heterometallic units and structurally similar metal cores. This heterometallic unit is composed of two peripheral metal-containing moieties {M(O2CR)3} struc* Dedicated to Academician of the Russian Academy of Sciences A. M. Muzafarov on the
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