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Review

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

by
Viktor I. Saloutin
1,
Yulia O. Edilova
1,
Yulia S. Kudyakova
1,
Yanina V. Burgart
1 and
Denis N. Bazhin
1,2,*
1
Postovsky Institute of Organic Synthesis, The Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620108, Russia
2
Department of Organic and Biomolecular Chemistry, Ural Federal University Named after the First President of Russia B.N. Yeltsin, Ekaterinburg 620002, Russia
*
Author to whom correspondence should be addressed.
Molecules 2022, 27(22), 7894; https://doi.org/10.3390/molecules27227894
Submission received: 7 October 2022 / Revised: 11 November 2022 / Accepted: 11 November 2022 / Published: 15 November 2022
(This article belongs to the Special Issue Synthesis, Characterization and Applications of Organometallic Complexes)
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Abstract

:
This review summarizes the data on the synthesis of coordination compounds containing two or more different metal ions based on fluorinated β-diketonates. Heterometallic systems are of high interest in terms of their potential use in catalysis, medicine and diagnostics, as well as in the development of effective sensor devices and functional materials. Having a rich history in coordination chemistry, fluorinated β-diketones are well-known ligands generating a wide variety of heterometallic complexes. In this context, we focused on both the synthetic approaches to β-dicarbonyl ligands with additional coordination centers and their possible transformations in complexation reactions. The review describes bi- and polynuclear structures in which β-diketones are the key building blocks in the formation of a heterometallic framework, including the examples of both homo- and heteroleptic complexes.

Graphical Abstract

1. Introduction

Combining different metals in coordination structures and inorganic matrices is a concept of high research interest. Its driving force originates not only from the attractive diversity of molecular structures, but mainly from their exceptional physicochemical properties. Organic ligands are crucial for the successful formation of heterometallic coordination complexes with a discrete or polymeric structure [1,2,3,4,5,6,7]. The possible applications of these compounds are widely investigated in catalytic processes [3,5] and in the search for new luminescent and magnetic materials [4,6], sensors [2,3,7], biologically active agents [1,7], etc.
Being able to form complexes with most of the elements of the periodic table, β-diketones occupy an important place among organic ligands [8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26]. Moreover, varying substituents at the β-dicarbonyl fragment is an effective tool for the fine-tuning of the physicochemical properties of coordination compounds. In particular, the introduction of one or two fluorinated substituents decreases the intermolecular interactions, thereby reducing the sublimation temperature of the complexes. Along with their thermal stability, these compounds are in high demand in the search for precursors for chemical deposition processes [27]. However, the prevalence of trifluoromethyl β-diketonates compared with non-fluorinated analogues is due to the increased solubility of their complexes and, therefore, the better crystallization [27].
Several reviews have reported the use of β-diketonates as precursors for MOCVD [27,28]. Examples of metal-containing molecular architectures incorporating β-diketonate motifs are described as luminescent materials [29,30]. The achievements in the field of supramolecular metal-containing structures based on poly-β-diketonate ligands are reviewed regularly [9,21,24,25].
This review aims to consider the fluorinated β-diketonates and their involvement in the synthesis of heterometallic structures. Such systematization will reveal the main advantages of the β-diketonates’ chemistry and demonstrate the features of polynuclear systems’ formation and their physicochemical properties.

2. Overview of Fluorinated β-Diketones Used as Ligands

The most common fluorinated β-diketones are illustrated in Figure 1. In this series, hfac is the most used ligand: it represents the acac derivative in which the methyl groups are replaced by trifluoromethyl substituents. Containing trifluoromethyl and thiophene substituents, tta is a preferred coligand in the design of luminescent and magnetic complexes. The trifluoromethyl group predominates among the other β-dicarbonyl backbone substituents in the structures of the known fluorinated β-diketonates involved in the synthesis of homo- and heteroleptic complexes.

3. The Synthesis of Fluorinated Ligands, Containing the β-Dicarbonyl Fragment

In this part, we show the approaches to the original fluorinated β-diketones, which were further used in the synthesis of heterometallic complexes. The Claisen condensation is known as the main synthetic method for the preparation of fluorinated β-diketones. The most frequently used condensing agents are NaH [31,32,33,34,35] and MeONa [36,37,38,39,40,41,42,43], while LiH [44,45,46,47,48], LDA [49] and Na [50] are less demanded. Ethers (DME, Et2O, THF) are more preferred solvents rather than benzene or alcohols. The synthesis of functionalized ligands incorporating the β-dicarbonyl fragment and fluorinated groups is shown in Scheme 1 [51,52,53,54,55,56,57]. In this case, the condensation proceeds between the fluorine-containing esters and methyl ketones bearing an aryl, hetaryl substituent or a functional group.
Trifluoromethylated β-diketone (HL9) with a bulky substituent bearing a methoxy group was obtained as a result of a multi-stage synthesis (Scheme 2) [58]. Alkylation with dimethyl-substituted propargyl alcohol (1) resulted in acetylene (2) containing a methoxy group at a tertiary carbon atom. Further trifluoroacetylation of unsaturated ether (2) gave alkoxyenone (3) that reacted with aniline to form the corresponding enaminoketone (4). At the last stage, an asymmetric diketone HL9 was isolated under acid hydrolysis.
Bazhin et al. later developed a more convenient approach to the synthesis of the methoxy-substituted β-diketone analogue [59]. For this purpose, a commercially available 2,3-butanedione (5) was used, in which one of the carbonyl groups can be easily transformed into an acetal fragment (Scheme 3). Further Claisen condensation of the obtained functional ketone (6) with fluorinated esters gave the acetal-containing lithium β-diketonates LiL [60,61]. The resulting lithium derivatives are easy to isolate in a pure form; they are stable and can be stored under normal conditions. However, these lithium salts were readily converted into 5-(perfluoroalkyl)furan-3(2H)-ones (7) under weakly acidic conditions and in the presence of the strong Lewis acids (e.g., BF3·Et2O) [45,46,59]. On the other hand, the direct coordination of lithium β-diketonates with metal ions did not require any bases. Moreover, an efficient method for replacing lithium with another alkali metal ion by the action of the corresponding fluoride was proposed (Scheme 3) [62].
To synthesize a C6F5-substituted β-diketone, the reaction between pentafluorobenzoyl chloride (8) and vinyl acetate was carried out in the presence of aluminum(III) chloride (Scheme 4) [63,64]. The condensation was accompanied by side products: an asymmetric β-diketone (9) with one perfluorophenyl substituent and a fluorinated chromone (10) derived from intramolecular cyclization. Aluminum(III) β-diketonate Al(L14)3 easily reacted with divalent transition metal ions (copper, cobalt, nickel) [63], thereby avoiding the isolation of the corresponding bis(pentafluorobenzoyl)methane (HL14) unstable in a free form.
The above analysis showed the structures of fluorinated 1,3-diketones used as ligands in the synthesis of organometallic derivatives are limited. In this context, functionalized 1,3-dicarbonyl compounds are the least studied, although they have much potential for the formation of heterometallic complexes.

4. Coordination Modes of Fluorinated β-Diketonates

The variety of coordination structures based on β-diketones arises from their ability to act as bi- and polydentate ligands, depending on the metal ions and coligands used [27]. Moreover, the fluorine atoms of the substituent in the β-dicarbonyl framework can participate in the extra coordination with metal ions. In this case, the interatomic distance M…F is less than the sum of the van der Waals radii of fluorine and metal ions indicating non-covalent interaction between them. The principal coordination modes of fluorinated β-diketonates are shown in Figure 2.

5. Heterometallic Complexes Containing Bridging β-Diketonate Anions

The co-crystallization of β-diketonates with various metal ions is known as one of the available methods for the synthesis of heterometallic compounds with both discrete and polymer coordination structures. For example, Lindoy et al. described the heterometallic complex [Eu-Co] (11) based on 3d and 4f metal β-diketonates: the stoichiometric structure was formed from two β-diketonates containing europium(III) and cobalt(III) in a CDCl3 solution (Scheme 5) [65]. In this case, oxygen atoms of non-fluorinated β-diketonate acted as bridging atoms between two metal ions (Figure 3).
The reaction of the iron(II) chloride and the fluorinated lithium β-diketonate led to a tetranuclear heterometallic complex [Li-Fe(II)] (12) (Scheme 6) [66]. The resulting iron(II) bis-β-diketonates were coordinated with two molecules of the initial lithium β-diketonate (Figure 4). The coordination environment of metal centers [LiO5] and [FeO6] consisted only of the oxygen atoms of β-diketonate anions without involving the fluorine atoms.
In the synthesis of polynuclear heterometallic complexes 13–17, alkali metal ions act as binders between two fragments of transition metal β-diketonates [67,68]. The initial reagents for these transformations are transition metals(III) β-diketonates based on acac, fluorine-containing sodium β-diketonates and chlorides of divalent 3d metal ions (Scheme 7, Figure 5, Figure 6 and Figure 7). The replacement of one CF3 group in the fluorinated ligand with a sterically bulky t-butyl group enables the number of metal atoms to be increased from three to five in the complex (Figure 6 and Figure 7). The assembly of trimetallic complexes 13, 14 was based on the transition metal ions of different oxidation states. In this case, the metal(III) ion was coordinated to non-fluorinated β-diketonate, which was not exchanged for hfac during the reaction.
The co-crystallization of two 3d β-diketonates with metals in different oxidation states resulted in [FeIII(acac)3][MnII(hfac)2] (18) and [NiII(hfac)2][FeIII(acac)3][NiII(hfac)2] (19) (Scheme 8) [69]. Similarly to heterometallic complexes 13–17, fluorinated β-diketonate was coordinated to a metal ion with the lowest oxidation number. In the structures of 18, 19 the oxygens of non-fluorinated β-diketonate were bridging atoms, which filled the coordination sphere of Mn(II) or Ni(II) ions coordinating the hfac (Figure 8 and Figure 9). Authors have postulated that the transition metal(II) center participating in bridging interactions with oxygen atoms of neighboring unit(s) should be highly Lewis acidic because of the chelation by diketonates with electron-withdrawing groups. In contrast, the transition metal(III) counterpart should have sterically uncongested ligands with electron-donating substituents provoking diketonate oxygen atoms’ involvement in bridging interactions with the M(II) center.
The solid-state reaction of precursors containing metals of different oxidation states led to heteroleptic [Bi(III)-M(II)] (20–22) complexes, where M(II) was a 3d transition metal ion (Scheme 9) [70]. In this case, the bridging oxygen atoms between metal centers were from the hfac ligands of the anionic tris-diketonate fragment (Figure 10).
Dikarev et al. described the first example of the heterometallic [Na-Cu] complex (22) resulting from two different fluorinated β-diketonates [64]. The reaction of unsolvated [Cu(L14)] and Na(hfac) gave a heterometallic β-diketonate [Na2Cu2(pfbm)4(hfac)2] (22) (Scheme 10). The discrete structure of the solvent-free [Na-Cu] environment consisted of a dimeric [Na2(hfac)2] unit surrounded by two Cu(pfbm)2 fragments (Figure 11). β-diketonates adopted the chelating-bridging mode between Cu and Na by coordinating through one oxygen atom in the case of F-aryl-containing ligands and two oxygen atoms in the case of hfac anions. The overall distorted square antiprismatic coordination environment for Na was formed by the five primary Na–O interactions (av. 2.41 Å) and three secondary Na–F contacts (av. 2.60 Å).
The methoxy substituent in thd, L9, L10, participated in the additional coordination with metal ions during the formation of polynuclear structures [71,72,73]. The co-crystallization of two different β-diketonates led to the discrete heterometallic complexes, e.g., [Pb-M] (23–26) (Figure 12). The thd is the unique structure because it contains a sterically bulky group close to the β-dicarbonyl fragment that is a necessary condition for the synthesis of discrete heterometallic complexes. If this does not happen, then coordination [Pb-Cu] polymers are formed in the absence of methoxy substituents at the β-dicarbonyl fragment [73,74]. In polymeric fluorinated [Pb-Cu] structures 23–26, the square planar chelate Cu(dik)2 built up an octahedral coordination environment due to the bridging oxygen atoms of the ligands from Pb(hfac)2 moieties.

6. Lanthanide(III) tetrakis-β-Diketonates

In general, the reaction of β-diketones with lanthanide(III) salts leads to the substitution of halide, carboxylate and nitrate anions of metals with a β-diketonate anion. The coordination of transition trivalent 4f-metals with two or three β-diketonate anions provided the discrete neutral complexes [M(dik)3(coligand)2] (Scheme 11) [25,29,32,33,39,75,76,77]. However, the metal ion was additionally coordinated to the solvent molecules or bidentate ligands having the donor heteroatoms (oxygen, nitrogen). At the next step, the metal(III) tetrakis-β-diketonates containing the anionic part of [M(dik)3]− or [M(dik)4]−,were formed as a result of the β-diketonate anion addition to the central metal atom in neutral tris-β-diketonates.
Biheterometallic tetrakis-β-diketonates can form both the discrete or polymer structures depending on the nature of the substituents in β-diketonate and coligands [78,79,80,81,82,83,84,85]. In the polymer chains 27–30, alkali metal ions, including sodium, potassium and cesium, acted as linkers between two adjacent tetrakis-β-diketonate fragments (Figure 13) [78,79,80,81]. In this case, both the oxygen and fluorine atoms of the β-diketonate were coordinated to alkali metals. A polyether molecule can be used as a polydentate coligand to fill the coordination environment of the alkali metal ion (28) [80]. The complexes Na[Ln(hfac)4] (27) were found to be highly volatile and stable in the gas phase while preserving the heterometallic fragment. The decay of heterometallic [Ln-Na] complexes (27) under argon atmosphere yielded the phase-pure NaLnF4 [78]. Varying the decay temperature, the formation of one of the NaLnF4 allotropes can be controlled [78]. Another approach was to use two precursors [Na(hfac)(tetraglyme)] and [Ln(hfac)3(diglyme)] together in sol–gel synthesis of the hexagonal phase of β-NaYF4:Yb3+,Er3+ at an elevated temperature [84].
Diketone HL7 with a pyrazole substituent formed the crystal packing of the heterometallic [Eu-Cs] complex (31) due to the coordination of nitrogen atoms of the heterocyclic system with cesium ions (Figure 14) [82]. The coordination environment of cesium(I) ions is saturated by nitrogen atoms of pyrazole, fluorine atoms of CF3 groups and bridging oxygen atoms of diketonate anions. The contact length of Cs…F is ~3.21–3.44 Å, which is comparable with the bond length of Cs…N equal to ~3.17–3.20 Å.
The complexation of ntfa with europium(III) chloride in the presence of sodium alkali in methanol gave the discrete [Eu-Na] tetrakis-β-diketonate (32) containing an acetyl naphthalene (Scheme 12) [83]. The aromatic ketone in the complex 32 indicates a side retro-Claisen reaction involving ntfa. Therefore, coligand contribution led to the change from polymer to discrete tetrakis-β-diketonates (Figure 15). Heterometallic complex 32 had good luminescent properties, exhibiting a phosphorescence time equal to 0.595 ms with a quantum yield of 47.5%. Photophysical parameters were measured under excitation at a wavelength of 370 nm in CH2Cl2 solution [83].
Succinimide can replace one of the water molecules from the coordination environment of alkali metal ions, thereby acting as coligand in heterometallic complex 33 (Figure 16) [85]. Tetrakis-β-diketonate [Eu-Na] (33) based on tta exhibited the high phosphorescence quantum yield of 71% and the afterglow time of 0.84 ms upon excitation at a wavelength of 365 nm.
The functionalized lithium β-diketonate LiL10 reacted with lanthanide(III) ions to form heterometallic compounds of various structures (Scheme 13) [62,86,87,88,89]. An extra functional group in the ligand saturated the metal ion coordination sphere with no additional coligands. Such homoleptic [Ln2L6] complexes (34) were obtained in the case of Ln(III) ions with the largest radius. However, the reaction of lithium diketonate LiL10 with most of the 4f metals led to the discrete β-diketonates 36–38 of three types depending on the solvent used (Scheme 13). The first type included “classical” tetrakis-β-diketonates 35, in which four β-diketonate anions were coordinated to lanthanide(III) ion. The methoxy groups of the ligands participate in the additional coordination with the lithium ion, thereby providing the discrete structure of 35 (Figure 17). The [Ln-Li] tetrakis-β-diketonates 35 were formed in acetonitrile media and the solvent molecule was also included in the crystal packing. Heterometallic complexes 35 were the first examples of lanthanide-lithium β-diketonates, which have been obtained and characterized by different spectral and crystallographic methods.
The second and the third types of complexes included the compounds 36, 37, in which the Ln(III) tris-β-diketonate fragment was coordinated to the initial lithium β-diketonate LiL10 (Scheme 13). The solvent choice (methanol or ethanol) influenced the coligands at the lithium ion in heterometallic complexes 36 (where Ln = Tb, Dy, Eu) (Figure 18). However, the main distinctive characteristic of these close structures was their different crystal packings. Complexes 36 (where Ln = Tb, Dy, Eu) exhibited mechanoluminescent properties, and one of them, [Dy-Li], was found to be a single-molecule magnet with an energy barrier equal to 53 K.
The exception was the trimetallic complex 38 formed by LiL10 reaction with praseodymium(III) nitrate (Scheme 14) [86]. Its structure contained a ten-coordinated praseodymium(III) ion and two lithium ions in the coordination with four β-diketonate anions (Figure 19). One of the ligands from the tris-β-diketonate fragment was bound with the lithium atom of the initial molecule LiL10. The coordination environment around the praseodymium(III) ion was saturated by nitrate and three β-diketonate anions, one methoxy group and the bridging oxygen atom of the LiL10 β-dicarbonyl fragment. In addition, an unusual structure of complex 38 included the second lithium ion, which was coordinated to methoxy groups and oxygen atoms from the β-diketonate fragment (Figure 19).
Increasing the length of the fluoroalkyl substituent from CF3 to C2F5 in acetal-containing β-diketonates LiL11 did not change the composition and structure of the resulting heterometallic β-diketonate 39 (Scheme 14, Figure 20) [89]. However, the phosphorescence lifetime decreased for the obtained [Tb-Li] diketonate 39 compared with the trifluoromethyl analog.
The acetal-containing β-diketonates of other alkali metals (Na, K, Cs) reacted with terbium(III) chloride to afford the [Tb-M] (M = Na, K, Cs) complexes 40–42 (Scheme 15) [62]. In all cases, the lanthanide(III) tetrakis-β-diketonates 40–42 were formed. Complex [Tb-Na] 40 had a discrete structure, while [Tb-K] 41 and [Tb-Cs] 42 were coordination polymers (Figure 21).

7. Heteronuclear Complexes with Isolated Metal Centers

This part describes complexes in which metal centers are not connected by bridging oxygen atoms of both β-diketonates and other coligands.
The co-crystallization of equimolar amounts of Dy(III) and Cu(II) β-diketonates afforded the heterometallic complex 43 in a good yield (Scheme 16) [90]. Coligands’ exchange around metal ions did not occur in this case (Figure 22). The Cu…Dy had the smallest distance between metal centers in the crystal lattice equal to 5.874 Å. Unlike the original [Dy(hfac)3•2H2O] complex, a synthesized [Dy-Cu] system (43) consisting of mixed β-diketonate ligands exhibited the properties of a molecular magnet with an energy barrier value equal to 55.3 K [90].
The solid-state redox reaction between tin(II) and 3d metal β-diketonates proceeded with the ligand exchange around the metal centers to give the heterometallic compounds 44–46 (Scheme 17) [91]. The obtained bimetallic complexes consisted of two homoleptic tris-β-diketonate fragments forming an ion pair (Figure 23).
Copper(II) β-diketonate reacted with tin(II) alkoxide to give the six-nuclear [Sn-Cu] complex (47) (Scheme 18) [92]. Similarly to bimetallic [Sn-M] complexes 44–46, an ion pair was formed as a result of the redox reaction. Copper(II) tris-β-diketonate represented the anionic part, while the oxygen atoms of tin(II) alkoxides were coordinated to copper(I) ions in the cationic part (Figure 24).

8. Binuclear Complexes Based on β-Diketones with an Additional Chelating Cavity

The fluorinated β-diketonates with 2,2′-bipyridinyl or phenanthrolinyl substituents (HL2, HL3) were used in the two-step synthesis of bimetallic [Ir-Eu] complexes 48, 49 (Scheme 19) [52,53,93,94]. At the first stage, only the 2,2′-bipyridinyl fragment of the ligand coordinated the Ir(III) ion. Furthermore, three β-diketonate anions 48, 49 with sterically congested iridium(III) fragments were involved in the coordination with lanthanide(III) ions. The resulting compounds 50, 51 demonstrate the rare examples of seven-coordinated Ln(III) ions with the [LnO6Cl] coordination environment (Figure 25). The structural differences of coordination centers promoted the assembly of heteroleptic Ln(III)-Ir(III) (Ln = Eu, Nd, Yb, Er, Gd) complexes [52,53,93,94]. As a result, heterometallic [Ir-Eu] compounds 50, 51 with bpy fragments demonstrated the higher values of phosphorescence lifetimes (up to 440 μs) compared with phen analogs. Replacing the CF3 group with C2F5 substituent slightly shifted the triplet state in [Ir-Eu] complexes towards the higher side [52]. Therefore, the C2F5-diketonate modified by bpy moiety represents an example of the efficient europium(III) sensitization through the excitation transferring from the Ir(III) to Eu(III) center [52].

9. Metallocene-Containing Heterometallic β-Diketonates

Metallocene derivatives are convenient molecules for the synthesis of heterometallic compounds with predictable composition and structure. One of the approaches is based on the co-crystallization of the modified ferrocene with transition metal β-diketonates. For example, 1,2-di(4-pyridylthio)ferrocene in reaction with Cu(hfac)2 gave 1D coordination polymer [Cu-Fe] (51) (Figure 26) [95].
Unsubstituted metallocenes can also form the polynuclear structures. Cobalt (I) cyclopentadienyl (Cp2Co), acting as a cation in heterometallic Ln(III) tetrakis-β-diketonates, afforded a complex 53 with uncoordinated counterions (Figure 27) [96]. The formation of a similar compound as a by-product was observed during the reaction between a binuclear lanthanide complex [Ln2(hfac)6(bptz)] (52) (where bptz–3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) and Cp2Co (Scheme 20).
The β-diketones HL15 reacted with Ln(III) chloride in the presence of triethylamine in methanol at room temperature to yield the clusters 54 containing four 4f metal ions decorated with ferrocene rings (Scheme 21) [97]. The organic base promoted the deprotonation of methanol and water molecules followed by the formation of a tetranuclear lanthanide(III) framework due to methanolate and hydroxide anions, which act as O-bridging ligands (Figure 28).
The reaction of diketone HL16 with aluminum(III) sulfate in methanol in the presence of aqueous ammonia resulted in the aluminum tris-β-diketonate 55 in 32% yield (Scheme 22) (Figure 29) [99]. The cytotoxicity of complex 55 against the human HeLa neoplastic cells was investigated: it was about 5 times less cytotoxic than the neutral diketone and approximately 50 times less toxic compared with a reference drug cisplatin.
The heterometallic [Cu-Fe] complex 56 was isolated in a good yield (45%) from the reaction of HL16 with [CuCl(PPh3)] in the presence of potassium tert-butylate in ether at room temperature (Scheme 23) [98]. Complex 56 showed the irreversible oxidation of Cu(I) centers to Cu(II) under anaerobic electrochemical conditions accompanied by the loss of PPh3 coligands and the formation of bis-diketonate [Cu(L16)2].
The synthesis of [Rh-Fe] complexes 59 included several stages with the step-by-step replacement of coligands at the Rh(I) ion (Scheme 24) [100]. Compounds 59 have been shown to provide the formation of Rh(I) active centers on the surfaces for heterogeneous catalysis. Silanol groups grafted on a solid matrix primarily replaced the β-diketonate anions in [Rh-Fe] complexes.
The oxidative addition of methyl iodide to the [Rh-Fe] compound 59 proceeded under mild conditions to afford the Rh(III) complex 60 in 90% yield (Scheme 25, Figure 30) [101]. Based on spectral data, the authors postulate that methyl-containing complex 60 and its acyl derivative exist in equilibrium with each other. However, since the 19F NMR spectra have not been registered, the transformations of the β-dicarbonyl framework accompanied by the isomers’ formation can proceed as well.
Sodium carbonate reacted with [CpIr(hfac)Cl] (61) in methanol under normal conditions to give an unusual heterotrimetallic complex (62) (Scheme 26) [102]. This transformation resulted in a hydroxycluster [CpIr(III)] coordinating the fluorinated sodium β-diketonate and free hfac (Figure 31).

10. Heteroleptic Complexes Involving β-Diketonates and Polytopic Coligands

The trifluoromethyl β-diketone HL1 with dithienylethene substituent was used as a ligand in the synthesis of heterometallic [Yb-Ru] complex 63 exhibiting the redox/optical control of emission (Figure 32) [51]. The bimetallic complex 63 was formed due to the coordination of the tris-β-diketonate Yb(L1)3 fragment with the functionalized 2,2′-bipyridine containing a ruthenium(III) ion.
The Schiff base with two different coordination modes formed the heterometallic 3d-4f binuclear complexes 65 (Scheme 27) [103,104]. The lanthanide(III) ions had an [LnO8] environment, whereas 3d metals ions preferably coordinated with the less “hard” nitrogen centers (Figure 33). The complexes with a combination of anisotropic Co(II) or Ni(II) ions with Tb(III) exhibited slow magnetic relaxation at low temperatures and, therefore, represented promising structures for single-molecular magnets’ design [103]. On the other hand, the heterometallic complexes containing Zn(II) and Tb(III) or Eu(III) ions showed luminescent properties [104]. In this case, the replacement of the bridging acetate anion by 1-pyrenbutanoic acid (complex 66, Figure 33) reduced the phosphorescence lifetime.
The co-crystallization of copper(II) β-diketonate with palladium(II) bis-enaminoketonate led to the heterobimetallic [Cu-Pd] complex 67 [105]. The bridging oxygen atoms of bis-enaminoketone between palladium(II) and copper(II) ions formed a discrete binuclear framework of the complex 67 (Figure 34).
Due to deprotonation of the hydroxy group, 8-hydroxyquinoline acted as a bridging ligand in the reaction with transition metal β-diketonates resulting in the homobimetallic complexes (Scheme 28) [106,107,108]. However, in the presence of a chromium(III) ion a trimetallic complex 68 was formed, in which a bridging phenolate anion connected the different metal ions (Figure 35) [108].
Heterometallic polymer complexes 69–71 including Eu(III) tris-β-diketonate fragments were synthesized based on the bidentate O,N-ligand–4-pyridyldiphenylphosphinoxide (Scheme 29) [109]. Polymer chains of 69–71 were formed through the coordination of phosphinoxide oxygen atom with Eu(hfac)3, whereas the nitrogen atom of the pyridine core bound the Pd(II), Zn(II) or Al(III) centers. Among the synthesized luminescent bimetallic polymers, complex [Eu-Al] 70 exhibited the highest value of the phosphorescence quantum yield equal to 72%.
The simultaneous addition of 3d and 4f β-diketonate hydrates to the reaction with nitronyl nitroxyls gave the heterometallic complexes 72–75 [110,111,112]. The coordination of 3d β-diketonate with the nitroxyl radical was accompanied by the Ln(III) tris-β-diketonate transformation into the corresponding Ln(III) tetrakis-β-diketonate anion (Figure 36) [110,111,112].
In most cases, the co-crystallization of 3d and 4f β-diketonates proceeded in the presence of the aza-heteroaryl-substituted nitronyl nitroxyls to provide the additional coordination centers with metal ions (Figure 37) [113,114,115,116,117,118,119]. The Ln(III) center predominantly formed an [LnO8] environment due to both the β-diketonate anions and nitroxyl oxygen atoms. In turn, 3d metal bis-diketonates were coordinated by either two nitrogen atoms of the heterocyclic substituents in a ligand or a nitroxyl oxygen atom and aza-heterocycle.

11. Heterometallic Complex Synthesis Based on hfac Transformations

In general, the synthesis of mono- and polynuclear β-diketonates is realized under basic conditions to facilitate the coordination with metal ions via deprotonation of the initial β-dicarbonyl compounds. Along with this, in some cases the base action provokes the β-diketone participation in the hydration process, retro-Claisen reaction or template transformations to form the metal complexes including tfa or ttpt as coligands [81,102,120,121,122,123,124,125,126,127,128,129,130].
A strong base used in the formation of a β-diketonate anion caused the destruction or transformation of the initial β-diketone. In work [126], the deprotonation with sodium hydroxide resulted in two possible routes of the retro-Claisen reaction (Scheme 30). Surprisingly, in the presence of two different carboxylates, a tetranuclear [Eu-Na] complex (84) was formed, including the β-diketonate anions and tris(3,5-dimethyl-1-pyrazolyl)methane (tpm) (Figure 38). The main phosphorescence characteristics were determined for the complex 84: the observed lifetime was 0.68 ms with a quantum yield of 39% and quantum efficiency equal to 58% [126].
The synthesis of heterometallic [Ni-Ln] complexes (83–87) included the two steps: Schiff base interaction with nickel(II) nitrate followed by the Ln(hfac)3 addition (Scheme 31) [127]. In that case, one fluorinated β-diketonate molecule from Ln(hfac)3 underwent a retro-Claisen reaction to give the [Ni-Ln] complexes (85–89) with the trifluoroacetate anion as coligand (Figure 39).
The nitrogen base, as an initial part of the complex, can further participate in the co-crystallization with fluorinated β-diketonate [129]. In particular, the tetranuclear bimetallic complex 91 was obtained by the reaction of Cd(pymt)2(phen)2 (90) with Cu(hfac)2 in acetonitrile (Scheme 32) [129]. The heterometallic structure 91 was formed based on the ttpt derived from hfac. Cadmium(II) both coordinated the diketonate anion and built a heterometallic framework of 91 due to the bridging oxygen atoms of ttpt (Figure 40). In addition, three hydroxyl oxygen atoms of two tpt and phen molecules formed the [CuO3N2] coordination environment of copper(II) ions.
After the decomplexation of heteronuclear [Cu-Cd] complex 91, all hydroxyl groups of tris-CF3-tetrahydropyran-2,4,6-triol were in the cis-configuration based on XRD data [129]. The proposed mechanism of pyran formation involves a retro-Claisen reaction followed by a condensation of trifluoroacetone enol with fluorinated copper diketonate (Scheme 33). Obviously, the triol formation led to the assembly of the tetranuclear [Cu-Cd] core, while the oxygen atoms of the hydroxyl groups in ligand acted as bridging atoms between metal ions. The other bases, including DMF, diethylformamide, formamide and sodium hydroxide, can also be used in the template reaction affording the ttpt.
The Hhfac cleavage accompanied by the trifluoroacetate formation proceeds easily under the action of tertiary amines at room temperature [131]. The reaction between Ln(hfac)3 and 1,3-bis(dimethylamino)-2-propanol (bdmap) leads to heteronuclear [Pr-Cu] complexes 93, 94 (Scheme 34). If copper(II) methoxide is reacted with Pr(hfac)3 instead of the corresponding acetate, trifluoroacetate and trifluoromethylated dioxane-diol (CF3-diol) are formed as coligands (Figure 41). The CF3-diol is formed due to the condensation reaction of trifluoroacetone with β-diketonate from Pr(hfac)3 (Scheme 35). To prove the mechanism of heterometallic [Pr-Cu] complex (93) formation, the authors carried out the reaction of the copper(II) methoxide and Pr(hfac)3 with trifluoroacetic acid and proposed trifluoroacetone in the presence of bdmapH (Scheme 34).

12. Conclusions

The described analysis of the literature demonstrates the wide scope of fluorinated β-diketones in the synthesis of heterometallic compounds. In most cases, the available diketones with trifluoromethyl and perfluoropropyl substituents (hfac, fod) form polynuclear systems containing up to five different metal ions. Moreover, fluorinated β-diketones as coligands can be used in the design of the heterometallic architectures in combination with other organic polydentate molecules. However, the potential of coordination compounds containing two or more different metal ions has not been fully realized in terms of practice. This is mainly because of the limited number of transition metals used in the synthesis of heterometallic structures. The specific chemical properties of the initial β-diketones should be considered when planning conditions for the synthesis of coordination compounds. In particular, the action of bases causes the β-diketones’ destruction to form heteroleptic complexes. In this context, the directed synthesis of β-diketones containing additional coordination centers is a more attractive design strategy for the heterometallic complexes [51,52,53,93,94,132]. This area is promising for obtaining not only discrete structures but also 2D/3D organometallic polymers, which are of applied interest in the development of magnetic, fluorescent, catalytic or sensor devices. Therefore, using polydentate fluorinated β-diketonates allows the heterometallic composition of structurally diverse coordination compounds to be varied, which, in turn, may give rise to advanced materials with interesting physicochemical properties.

Author Contributions

Conceptualization, D.N.B., Y.S.K. and Y.V.B.; writing—original draft preparation, D.N.B., Y.O.E. and Y.S.K.; writing—review and editing, Y.O.E., Y.S.K., D.N.B. and Y.V.B.; visualization, Y.O.E.; supervision, V.I.S.; project administration, D.N.B. All authors have read and agreed to the published version of the manuscript.

Funding

This work was carried out in the framework of the basic theme of the Russian Academy of Sciences (state registration № AAAA-A19-119011290117-6).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

Abbreviations

MOCVDmetal organic chemical vapor deposition;
hfac1,1,1,5,5,5-hexafluoro-2,4-pentanedionate;
tfatrifluoroacetate;
tfac1,1,1-trifluoro-2,4-pentanedionate;
ptac1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate;
fod6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate;
ttathenoyltrifluoroacetylacetonate;
ftafuranoyltrifluoroacetylacetonate;
btabenzoyltrifluoroacetone;
ntfa4,4,4-trifluoro-1-(2-naphtyl)-1,3-butanedionate;
Na2EDTAethylenediaminetetraacetic acid disodium salt;
PTSAp-toluenesulfonic acid;
dikβ-diketonate;
acacacetylacetonate;
thd2,2,6,6-tetramethyl-3,5-heptanedionate;
pfbmbis(pentafluorobenzoyl)methane;
Cpcyclopentadienyl;
Fcferrocene;
DME1,2-dimethoxyethane;
DMFdimethylformamide;
Etethyl;
LDAlithium di(isopropyl)amide;
Memethyl;
THFtetrahydrofuran;
ttpttris-CF3-tetrahydropyran-2,4,6-triol;
bptz3,6-bis(2-pyridyl)-1,2,4,5-tetrazine;
phen1,10-phenantroline;
bdmap1,3-bis(dimethylamino)-2-propanol.

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Molecules 27 07894 g001 550
Figure 1. Structures of fluorinated β-diketonate ligands.
Figure 1. Structures of fluorinated β-diketonate ligands.
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Molecules 27 07894 sch001 550
Scheme 1. The synthesis of fluorinated functionalized β-diketones [51,52,53,54,55,56,57]. Reaction conditions: [a] LDA, THF, −78 °C, then HClaq; [b] Na, benzene, reflux; [c] NaH, THF, EtOH (cat.), then AcOH; [d] CaH2, MeOH, then Cu(OAc)2 followed by the decomposition with Na2EDTAaq.
Scheme 1. The synthesis of fluorinated functionalized β-diketones [51,52,53,54,55,56,57]. Reaction conditions: [a] LDA, THF, −78 °C, then HClaq; [b] Na, benzene, reflux; [c] NaH, THF, EtOH (cat.), then AcOH; [d] CaH2, MeOH, then Cu(OAc)2 followed by the decomposition with Na2EDTAaq.
Molecules 27 07894 sch001
Molecules 27 07894 sch002 550
Scheme 2. The synthesis of methoxy-substituted CF3-β-diketone.
Scheme 2. The synthesis of methoxy-substituted CF3-β-diketone.
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Molecules 27 07894 sch003 550
Scheme 3. The synthesis of fluorinated acetal-containing β-diketonates [59,60,61,62].
Scheme 3. The synthesis of fluorinated acetal-containing β-diketonates [59,60,61,62].
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Molecules 27 07894 sch004 550
Scheme 4. Synthesis of C6F5-substituted β-diketone.
Scheme 4. Synthesis of C6F5-substituted β-diketone.
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Figure 2. Possible coordination modes of fluorinated β-diketones.
Figure 2. Possible coordination modes of fluorinated β-diketones.
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Molecules 27 07894 sch005 550
Scheme 5. Synthesis of the heterometallic complex [Eu-Co] (11).
Scheme 5. Synthesis of the heterometallic complex [Eu-Co] (11).
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Figure 3. Molecular structure of 11. Hydrogen atoms and some methyl groups have been omitted, C3F7 groups of fod are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1100888.
Figure 3. Molecular structure of 11. Hydrogen atoms and some methyl groups have been omitted, C3F7 groups of fod are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1100888.
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Molecules 27 07894 sch006 550
Scheme 6. Synthesis of tetranuclear heterometallic complex [Li-Fe] (12).
Scheme 6. Synthesis of tetranuclear heterometallic complex [Li-Fe] (12).
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Molecules 27 07894 g004 550
Figure 4. Molecular structure of 12: (dik = ptac) [66]. Hydrogen atoms have been omitted, CF3 groups of ptac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1518385.
Figure 4. Molecular structure of 12: (dik = ptac) [66]. Hydrogen atoms have been omitted, CF3 groups of ptac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1518385.
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Molecules 27 07894 sch007 550
Scheme 7. Synthesis of polynuclear M(II)/M(III) β-diketonates [67,68].
Scheme 7. Synthesis of polynuclear M(II)/M(III) β-diketonates [67,68].
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Molecules 27 07894 g005 550
Figure 5. Molecular structure of 13 [67]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1964370.
Figure 5. Molecular structure of 13 [67]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1964370.
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Molecules 27 07894 g006 550
Figure 6. Molecular structure of 16 [68]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1998878.
Figure 6. Molecular structure of 16 [68]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1998878.
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Molecules 27 07894 g007 550
Figure 7. Molecular structure of 17 [68]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1998879.
Figure 7. Molecular structure of 17 [68]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1998879.
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Molecules 27 07894 sch008 550
Scheme 8. Synthesis of polynuclear M(II)/Fe(III) β-diketonates.
Scheme 8. Synthesis of polynuclear M(II)/Fe(III) β-diketonates.
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Molecules 27 07894 g008 550
Figure 8. Molecular structure of 18 [69]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1040552.
Figure 8. Molecular structure of 18 [69]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1040552.
Molecules 27 07894 g008
Molecules 27 07894 g009 550
Figure 9. Molecular structure of 19 [69]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1040553.
Figure 9. Molecular structure of 19 [69]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1040553.
Molecules 27 07894 g009
Molecules 27 07894 sch009 550
Scheme 9. Synthesis of heteroleptic [Bi(III)-M(II)] complexes (20–22).
Scheme 9. Synthesis of heteroleptic [Bi(III)-M(II)] complexes (20–22).
Molecules 27 07894 sch009
Molecules 27 07894 g010 550
Figure 10. Molecular structure of 21 [70]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1475305.
Figure 10. Molecular structure of 21 [70]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1475305.
Molecules 27 07894 g010
Molecules 27 07894 sch010 550
Scheme 10. Synthesis of heterometallic [Na-Cu] complex (22).
Scheme 10. Synthesis of heterometallic [Na-Cu] complex (22).
Molecules 27 07894 sch010
Molecules 27 07894 g011 550
Figure 11. Molecular structure of 22 [64]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1850164.
Figure 11. Molecular structure of 22 [64]. Hydrogen atoms have been omitted, CF3 groups of hfac are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1850164.
Molecules 27 07894 g011
Molecules 27 07894 g012 550
Figure 12. Molecular structures of 23–26 [71,72,73,74]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cifs have been retrieved from CCDC.
Figure 12. Molecular structures of 23–26 [71,72,73,74]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cifs have been retrieved from CCDC.
Molecules 27 07894 g012
Molecules 27 07894 sch011 550
Scheme 11. Synthesis of lanthanide(III) tris-/tetrakis-β-diketonates.
Scheme 11. Synthesis of lanthanide(III) tris-/tetrakis-β-diketonates.
Molecules 27 07894 sch011
Molecules 27 07894 g013 550
Figure 13. Molecular structures of Ln(III) tetrakis-diketonates 27–30 [78,79,80,81]. Hydrogen atoms and some CF3 groups have been omitted for clarity. The cifs has been retrieved from CCDC.
Figure 13. Molecular structures of Ln(III) tetrakis-diketonates 27–30 [78,79,80,81]. Hydrogen atoms and some CF3 groups have been omitted for clarity. The cifs has been retrieved from CCDC.
Molecules 27 07894 g013
Molecules 27 07894 g014 550
Figure 14. Structure X-ray structure of one-dimensional chain in 31 [82]. Hydrogen atoms have been omitted, some diketonate ligands and CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 922987.
Figure 14. Structure X-ray structure of one-dimensional chain in 31 [82]. Hydrogen atoms have been omitted, some diketonate ligands and CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 922987.
Molecules 27 07894 g014
Molecules 27 07894 sch012 550
Scheme 12. Synthesis of tetrakis-β-diketonate [Eu-Na] (32).
Scheme 12. Synthesis of tetrakis-β-diketonate [Eu-Na] (32).
Molecules 27 07894 sch012
Molecules 27 07894 g015 550
Figure 15. Molecular structure of 32 [83]. Hydrogen atoms have been omitted, some ligands groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 2071833.
Figure 15. Molecular structure of 32 [83]. Hydrogen atoms have been omitted, some ligands groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 2071833.
Molecules 27 07894 g015
Molecules 27 07894 g016 550
Figure 16. Molecular structure of 33 [85]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 2013280.
Figure 16. Molecular structure of 33 [85]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 2013280.
Molecules 27 07894 g016
Molecules 27 07894 sch013 550
Scheme 13. Synthesis of lanthanide(III) complexes based on lithium β-diketonate (LiL10).
Scheme 13. Synthesis of lanthanide(III) complexes based on lithium β-diketonate (LiL10).
Molecules 27 07894 sch013
Molecules 27 07894 g017 550
Figure 17. Molecular structure of 35 [87]. Hydrogen atoms, MeCN molecules have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers are 1973632 (Ln = Eu), 1973633 (Ln = Tb).
Figure 17. Molecular structure of 35 [87]. Hydrogen atoms, MeCN molecules have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers are 1973632 (Ln = Eu), 1973633 (Ln = Tb).
Molecules 27 07894 g017
Molecules 27 07894 g018 550
Figure 18. Molecular structures of 36 and 37 (dik = L10) [86,88]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC.
Figure 18. Molecular structures of 36 and 37 (dik = L10) [86,88]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC.
Molecules 27 07894 g018
Molecules 27 07894 g019 550
Figure 19. Molecular structure of 38 [86]. Hydrogen atoms have been omitted, CF3 groups and one ligand molecule are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 2031103.
Figure 19. Molecular structure of 38 [86]. Hydrogen atoms have been omitted, CF3 groups and one ligand molecule are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 2031103.
Molecules 27 07894 g019
Molecules 27 07894 sch014 550
Scheme 14. Synthesis of discrete [Tb-Li] diketonate 39.
Scheme 14. Synthesis of discrete [Tb-Li] diketonate 39.
Molecules 27 07894 sch014
Molecules 27 07894 g020 550
Figure 20. Molecular structure of 39 [89]. Hydrogen atoms have been omitted, C2F5 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 2011088.
Figure 20. Molecular structure of 39 [89]. Hydrogen atoms have been omitted, C2F5 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 2011088.
Molecules 27 07894 g020
Molecules 27 07894 sch015 550
Scheme 15. Synthesis of terbium(III) tetrakis-β-diketonates 40–42.
Scheme 15. Synthesis of terbium(III) tetrakis-β-diketonates 40–42.
Molecules 27 07894 sch015
Molecules 27 07894 g021 550
Figure 21. Molecular structures of 40–42 [62]. Hydrogen atoms have been omitted, some CF3 groups are transparent for clarity. The cif has been retrieved from CCDC.
Figure 21. Molecular structures of 40–42 [62]. Hydrogen atoms have been omitted, some CF3 groups are transparent for clarity. The cif has been retrieved from CCDC.
Molecules 27 07894 g021
Molecules 27 07894 sch016 550
Scheme 16. Synthesis of [Dy-Cu] β-diketonate 43.
Scheme 16. Synthesis of [Dy-Cu] β-diketonate 43.
Molecules 27 07894 sch016
Molecules 27 07894 g022 550
Figure 22. A crystal packing fragment of 43 [90]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1938913.
Figure 22. A crystal packing fragment of 43 [90]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1938913.
Molecules 27 07894 g022
Molecules 27 07894 sch017 550
Scheme 17. Synthesis of discrete [Sn(IV)-M(II)] complexes (44–46) [91].
Scheme 17. Synthesis of discrete [Sn(IV)-M(II)] complexes (44–46) [91].
Molecules 27 07894 sch017
Molecules 27 07894 g023 550
Figure 23. Molecular structure of 45 [91]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 1811494.
Figure 23. Molecular structure of 45 [91]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 1811494.
Molecules 27 07894 g023
Molecules 27 07894 sch018 550
Scheme 18. Synthesis of bimetallic [Sn-Cu] complex 47..
Scheme 18. Synthesis of bimetallic [Sn-Cu] complex 47..
Molecules 27 07894 sch018
Molecules 27 07894 g024 550
Figure 24. Molecular structure of 47 [92]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 1056284.
Figure 24. Molecular structure of 47 [92]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC numbers is 1056284.
Molecules 27 07894 g024
Molecules 27 07894 sch019 550
Scheme 19. Synthesis of bimetallic [Ir-Eu] complexes 48, 49.
Scheme 19. Synthesis of bimetallic [Ir-Eu] complexes 48, 49.
Molecules 27 07894 sch019
Molecules 27 07894 g025 550
Figure 25. Molecular structure of 50 [52]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 730200.
Figure 25. Molecular structure of 50 [52]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 730200.
Molecules 27 07894 g025
Molecules 27 07894 g026 550
Figure 26. A fragment of polymeric structure of 51 [95]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1556476.
Figure 26. A fragment of polymeric structure of 51 [95]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1556476.
Molecules 27 07894 g026
Molecules 27 07894 sch020 550
Scheme 20. Reaction of Dy2(hfac)6(bptz) with Cp2Co.
Scheme 20. Reaction of Dy2(hfac)6(bptz) with Cp2Co.
Molecules 27 07894 sch020
Molecules 27 07894 g027 550
Figure 27. Molecular structure of 53 [96]. Hydrogen atoms have been omitted, some ligands groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1811780.
Figure 27. Molecular structure of 53 [96]. Hydrogen atoms have been omitted, some ligands groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1811780.
Molecules 27 07894 g027
Molecules 27 07894 sch021 550
Scheme 21. Reaction of β-diketones HL15 with Ln(III) chloride [98].
Scheme 21. Reaction of β-diketones HL15 with Ln(III) chloride [98].
Molecules 27 07894 sch021
Molecules 27 07894 g028 550
Figure 28. Molecular structure of 54 [97]. Hydrogen atoms have been omitted, C2F5 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 984498.
Figure 28. Molecular structure of 54 [97]. Hydrogen atoms have been omitted, C2F5 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 984498.
Molecules 27 07894 g028
Molecules 27 07894 sch022 550
Scheme 22. Synthesis of tris-β-diketonate [Al-Fe] 55.
Scheme 22. Synthesis of tris-β-diketonate [Al-Fe] 55.
Molecules 27 07894 sch022
Molecules 27 07894 g029 550
Figure 29. Molecular structure of 55 [99]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 877638.
Figure 29. Molecular structure of 55 [99]. Hydrogen atoms have been omitted, CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 877638.
Molecules 27 07894 g029
Molecules 27 07894 sch023 550
Scheme 23. Synthesis of heterometallic [Cu-Fe] complex 56.
Scheme 23. Synthesis of heterometallic [Cu-Fe] complex 56.
Molecules 27 07894 sch023
Molecules 27 07894 sch024 550
Scheme 24. Synthesis of heterometallic [Rh-Fe] complex 59.
Scheme 24. Synthesis of heterometallic [Rh-Fe] complex 59.
Molecules 27 07894 sch024
Molecules 27 07894 sch025 550
Scheme 25. Transformation of heterometallic [Rh-Fe] complex 59.
Scheme 25. Transformation of heterometallic [Rh-Fe] complex 59.
Molecules 27 07894 sch025
Molecules 27 07894 g030 550
Figure 30. Molecular structure of 60 [101]. Hydrogen atoms have been omitted, CF3 group is transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 646438.
Figure 30. Molecular structure of 60 [101]. Hydrogen atoms have been omitted, CF3 group is transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 646438.
Molecules 27 07894 g030
Molecules 27 07894 sch026 550
Scheme 26. Synthesis of heterometallic [Ir-Na] complex 62.
Scheme 26. Synthesis of heterometallic [Ir-Na] complex 62.
Molecules 27 07894 sch026
Molecules 27 07894 g031 550
Figure 31. Molecular structure of 62 [102]. Hydrogen atoms have been omitted for clarity. The cif has been retrieved from CCDC. CCDC number is 1996249.
Figure 31. Molecular structure of 62 [102]. Hydrogen atoms have been omitted for clarity. The cif has been retrieved from CCDC. CCDC number is 1996249.
Molecules 27 07894 g031
Molecules 27 07894 g032 550
Figure 32. Molecular structure of 63 [51]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1959918.
Figure 32. Molecular structure of 63 [51]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1959918.
Molecules 27 07894 g032
Molecules 27 07894 sch027 550
Scheme 27. Synthesis of heterometallic 3d-4f binuclear complexes 65–66.
Scheme 27. Synthesis of heterometallic 3d-4f binuclear complexes 65–66.
Molecules 27 07894 sch027
Molecules 27 07894 g033 550
Figure 33. Molecular structure of 65, 66 (dik = hfac) [103,104]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC.
Figure 33. Molecular structure of 65, 66 (dik = hfac) [103,104]. Hydrogen atoms have been omitted, some ligand groups are transparent for clarity. The cif has been retrieved from CCDC.
Molecules 27 07894 g033
Molecules 27 07894 g034 550
Figure 34. Molecular structure of 67 [105]. The cif has been retrieved from CCDC. CCDC number is 1961116.
Figure 34. Molecular structure of 67 [105]. The cif has been retrieved from CCDC. CCDC number is 1961116.
Molecules 27 07894 g034
Molecules 27 07894 sch028 550
Scheme 28. Synthesis of heterometallic [Ln-Cr] complexes 68.
Scheme 28. Synthesis of heterometallic [Ln-Cr] complexes 68.
Molecules 27 07894 sch028
Molecules 27 07894 g035 550
Figure 35. Molecular structure of 68 [108]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 812496.
Figure 35. Molecular structure of 68 [108]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 812496.
Molecules 27 07894 g035
Molecules 27 07894 sch029 550
Scheme 29. Synthesis of polymers, containing Eu(III) and 3d metal ions.
Scheme 29. Synthesis of polymers, containing Eu(III) and 3d metal ions.
Molecules 27 07894 sch029
Molecules 27 07894 g036 550
Figure 36. The examples of 3d/4f complexes containing Ln(III) tetrakis-β-diketonate fragments. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC [110,111,112].
Figure 36. The examples of 3d/4f complexes containing Ln(III) tetrakis-β-diketonate fragments. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC [110,111,112].
Molecules 27 07894 g036
Molecules 27 07894 g037a 550Molecules 27 07894 g037b 550
Figure 37. (a)The examples of 3d/4f complexes containing Ln(III) tris-β-diketonate fragments. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. (b) The examples of 3d/4f complexes containing Ln(III) tris-β-diketonate fragments. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC [113,114,115,116,117,118,119].
Figure 37. (a)The examples of 3d/4f complexes containing Ln(III) tris-β-diketonate fragments. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. (b) The examples of 3d/4f complexes containing Ln(III) tris-β-diketonate fragments. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC [113,114,115,116,117,118,119].
Molecules 27 07894 g037aMolecules 27 07894 g037b
Molecules 27 07894 sch030 550
Scheme 30. Synthesis and proposed mechanism of heterometallic [Eu-Na] complex (84) formation.
Scheme 30. Synthesis and proposed mechanism of heterometallic [Eu-Na] complex (84) formation.
Molecules 27 07894 sch030
Molecules 27 07894 g038 550
Figure 38. Molecular structure of 84 [126]. Some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1008766.
Figure 38. Molecular structure of 84 [126]. Some ligand groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1008766.
Molecules 27 07894 g038
Molecules 27 07894 sch031 550
Scheme 31. Synthesis of heterometallic [Ln-Ni] complexes 85–89 [129].
Scheme 31. Synthesis of heterometallic [Ln-Ni] complexes 85–89 [129].
Molecules 27 07894 sch031
Molecules 27 07894 g039 550
Figure 39. Molecular structure of 87 [127]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1556429.
Figure 39. Molecular structure of 87 [127]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1556429.
Molecules 27 07894 g039
Molecules 27 07894 sch032 550
Scheme 32. Synthesis of heterometallic [Cu-Cd] complexes 91.
Scheme 32. Synthesis of heterometallic [Cu-Cd] complexes 91.
Molecules 27 07894 sch032
Molecules 27 07894 g040 550
Figure 40. The crystal structures of [Cu2(phen)2(ttpt)2Cd2(hfac)2] (91) [129]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 616292.
Figure 40. The crystal structures of [Cu2(phen)2(ttpt)2Cd2(hfac)2] (91) [129]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 616292.
Molecules 27 07894 g040
Molecules 27 07894 sch033 550
Scheme 33. The proposed mechanism of pyran formation from Cu(hfac)2.
Scheme 33. The proposed mechanism of pyran formation from Cu(hfac)2.
Molecules 27 07894 sch033
Molecules 27 07894 sch034 550
Scheme 34. Synthesis of polynuclear Pr(III) complexes via Hhfac transformations.
Scheme 34. Synthesis of polynuclear Pr(III) complexes via Hhfac transformations.
Molecules 27 07894 sch034
Molecules 27 07894 g041 550
Figure 41. Crystal structure of [Pr(hfac)2(CF3-diol)Cu(Hbdmap)2(tfa)] (93) [131]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1232922.
Figure 41. Crystal structure of [Pr(hfac)2(CF3-diol)Cu(Hbdmap)2(tfa)] (93) [131]. CF3 groups are transparent for clarity. The cif has been retrieved from CCDC. CCDC number is 1232922.
Molecules 27 07894 g041
Molecules 27 07894 sch035 550
Scheme 35. Proposed mechanism for trifluoromethylated dioxane-diol formation.
Scheme 35. Proposed mechanism for trifluoromethylated dioxane-diol formation.
Molecules 27 07894 sch035
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Saloutin, V.I.; Edilova, Y.O.; Kudyakova, Y.S.; Burgart, Y.V.; Bazhin, D.N. Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands. Molecules 2022, 27, 7894. https://doi.org/10.3390/molecules27227894

AMA Style

Saloutin VI, Edilova YO, Kudyakova YS, Burgart YV, Bazhin DN. Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands. Molecules. 2022; 27(22):7894. https://doi.org/10.3390/molecules27227894

Chicago/Turabian Style

Saloutin, Viktor I., Yulia O. Edilova, Yulia S. Kudyakova, Yanina V. Burgart, and Denis N. Bazhin. 2022. "Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands" Molecules 27, no. 22: 7894. https://doi.org/10.3390/molecules27227894

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