Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates

Double- and triple-decker lanthanide phthalocyaninates exhibit unique physical-chemical properties, particularly single-molecule magnetism. Among other factors, the magnetic properties of these sandwiches depend on their conformational state, which is determined via the skew angle of the phthalocyanine ligands. Thus, in the present work we report the comprehensive conformational study of substituted terbium(III) and yttrium(III) trisphthalocyaninates in solution depending on the substituents at the periphery of molecules, redox-states and nature of solvents. Conjunction of UV-vis-NIR spectroscopy and quantum-chemical calculations within simplified time-dependent DFT in Tamm–Dancoff approximation provided the spectroscopic signatures of staggered and gauche conformations of trisphthalocyaninates. Altogether, it allowed us to demonstrate that the butoxy-substituted complex behaves as a molecular switcher with controllable conformational state, while the crown-substituted triple-decker complex maintains a staggered conformation regardless of external factors. The analysis of noncovalent interactions within the reduced density gradient approach allowed to shed light on the nature of factors stabilizing certain conformers

Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities

The detailed knowledge about the structure of multinuclear paramagnetic lanthanide complexes for the targeted design of these compounds with special magnetic, sensory, optical and electronic properties is a very important task. At the same time, establishing the structure of such multinuclear paramagnetic lanthanide complexes in solution, using NMR is a difficult task, since several paramagnetic centers act simultaneously on the resulting chemical shift of a particular nucleus. In this paper, we have demonstrated the possibility of molecular structure determination in solution on the example of binuclear triple-decker lanthanide(III) complexes with tetra-15-crown-5-phthalocyanine Ln2[(15C5)4Pc]3 {where Ln = Tb (1) and Dy (2)} by quantitative analysis of the pseudo-contact lanthanide-induced shifts (LIS). The symmetry of complexes was used for the simplification of the calculation of pseudo-contact shifts on the base of the expression for the magnetic susceptibility tensor in the arbitrary oriented magnetic axis system. Good agreement between the calculated and experimental shifts in the 1H NMR spectra indicates the similarity of the structure for the complexes 1 and 2 in solution of CDCl3 and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu2[(15C5)4Pc]3. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes

Single-Molecule Magnets Based on Heteroleptic Terbium(III) Trisphthalocyaninate in Solvent-Free and Solvent-Containing Forms

Binuclear heteroleptic triple-decker terbium(III) phthalocyaninate (Pc)Tb[(15C5)4Pc]Tb(Pc), where Pc2− is phthalocyaninate dianion and 15C5 is a 15-crown-5 moiety, has been synthesized as a solvent-free powder (1) and a well-defined crystal solvate with o-dichlorobenzene (Pc)Tb[(15C5)4Pc]Tb(Pc)⋅6C6H4Cl2 (2). In the crystal structure of 2, the Tb-N(Pc) distances to the nitrogen atoms in the outer and inner decks are 2.350–2.367(4) and 2.583–2.598(4) Å, respectively, and the Tb–Tb distance is 3.4667(3) Å. The twist angle between the outer and the inner decks is 42.6°. The magnetic properties were studied for both 1 and 2. The χMT magnitude of 23.3 emu⋅K/mol at 300 K indicates a contribution of two TbIII centers with the 7F6 ground state. The χMT product increases with decreasing temperature to reach 38.5 emu⋅K/mol at 2 K. This is indicative of ferromagnetic coupling between TbIII spins in accordance with previous data for triple-decker lanthanide phthalocyaninates of a dipolar nature. Both forms show a single-molecule magnet (SMM) behavior manifesting the in-phase (χ′) and out-of-phase (χ″) AC susceptibility signals in an oscillating field of 3 Oe with estimated effective spin-reversal energy barriers (Ueff) of 222(9) and 93(7) cm−1 for 1 and 2, respectively. The compounds show narrow hysteresis loops in the −1 – +1 kOe range, and the splitting between the zero-field-cooling and field-cooling curves is observed below 6 K. Thus, in spite of similar static magnetic characteristics, each form of the Tb(III) complex shows a different dynamic SMM behavior

Single-Molecule Magnets Based on Heteroleptic Terbium(III) Trisphthalocyaninate in Solvent-Free and Solvent-Containing Forms

Binuclear heteroleptic triple-decker terbium(III) phthalocyaninate (Pc)Tb[(15C5)4Pc]Tb(Pc), where Pc2− is phthalocyaninate dianion and 15C5 is a 15-crown-5 moiety, has been synthesized as a solvent-free powder (1) and a well-defined crystal solvate with o-dichlorobenzene (Pc)Tb[(15C5)4Pc]Tb(Pc)⋅6C6H4Cl2 (2). In the crystal structure of 2, the Tb-N(Pc) distances to the nitrogen atoms in the outer and inner decks are 2.350–2.367(4) and 2.583–2.598(4) Å, respectively, and the Tb–Tb distance is 3.4667(3) Å. The twist angle between the outer and the inner decks is 42.6°. The magnetic properties were studied for both 1 and 2. The χMT magnitude of 23.3 emu⋅K/mol at 300 K indicates a contribution of two TbIII centers with the 7F6 ground state. The χMT product increases with decreasing temperature to reach 38.5 emu⋅K/mol at 2 K. This is indicative of ferromagnetic coupling between TbIII spins in accordance with previous data for triple-decker lanthanide phthalocyaninates of a dipolar nature. Both forms show a single-molecule magnet (SMM) behavior manifesting the in-phase (χ′) and out-of-phase (χ″) AC susceptibility signals in an oscillating field of 3 Oe with estimated effective spin-reversal energy barriers (Ueff) of 222(9) and 93(7) cm−1 for 1 and 2, respectively. The compounds show narrow hysteresis loops in the −1 – +1 kOe range, and the splitting between the zero-field-cooling and field-cooling curves is observed below 6 K. Thus, in spite of similar static magnetic characteristics, each form of the Tb(III) complex shows a different dynamic SMM behavior

Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln­(III) ion (for Y and almost the whole lanthanide family), [(15C5)₄Pc]­M*­[(15C5)₄Pc]­M­(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of ¹H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]synthesized by the above-mentioned method

Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln­(III) ion (for Y and almost the whole lanthanide family), [(15C5)₄Pc]­M*­[(15C5)₄Pc]­M­(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of ¹H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]synthesized by the above-mentioned method

Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln­(III) ion (for Y and almost the whole lanthanide family), [(15C5)₄Pc]­M*­[(15C5)₄Pc]­M­(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of ¹H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]synthesized by the above-mentioned method