TY - JOUR
T1 - Ferrocenyl-based di- and trinuclear lanthanide complexes
T2 - solid state structures, (spectro)electrochemical and DFT studies
AU - Khalladi, Ahmed
AU - Kovalski, Eduard
AU - Abdulmalic, Mohammad A.
AU - Rüffer, Tobias
AU - Yuan, Qing
AU - Naïli, H.
AU - Korb, Marcus
AU - Lang, Heinrich
N1 - Funding Information:
M. K. gratefully acknowledges support from the Forrest Research Foundation for a Forrest Research Fellowship. This research was undertaken with the assistance of computational resources from the KAYA high-performance computing cluster at the University of Western Australia, a facility funded by the University, State and Commonwealth Governments. The authors gratefully acknowledge the IT Infrastructure and Platforms – High Performance Computing team.
Publisher Copyright:
© 2023 The Royal Society of Chemistry.
PY - 2023/11/27
Y1 - 2023/11/27
N2 - Dinuclear and trinuclear ferrocenylcarboxylato-bridged lanthanide complexes of type [Ln(μO:κ2OO′-O2CFc)(O2CFc)2(H2O)(dmf)]2·(dmf)2 (Ln = Sm (2), Eu (3), Gd (4), Tb (5); Fc = Fe(η5-C5H4)(η5-C5H5)), and novel [Bu4N][Ln3(μ-O2CFc)3(μO:κ2OO′-O2CFc)3(O2CFc)3(μ3-OH)]·[Bu4N]Cl (Ln = Gd (6), Tb (7)) were prepared by the reaction of [LnCl3·6H2O] (synthesis of 2-5) or LnCl3 (synthesis of 6, 7) with FcCO2H (1) in the ratio of 1 : 3. As evidenced by single crystal X-ray structure determination, in 2-5 the lanthanide ions are connected by symmetric FcCO2 units. In addition, two ferrocenylcarboxylato groups are μ-bridged to LnIII. Each LnIII ion is coordinated by nine oxygen donor atoms derived from one H2O, one dmf and three carboxylates. The latter are found in chelating κ2 and bridging μ,κ3 coordination modes. Complexes 6 and 7 assemble three LnIII cores around a central μ3-netting hydroxide and nine FcCO2 entities. A combination of κ2, μ,κ2 and μ,κ3 coordination modes results in an eight-fold coordination sphere for each metal, which is best described as bicapped trigonal prismatic. IR spectroscopy confirms the chelating and bridging motifs. Electrochemical studies of complexes 2-7via cyclic voltammetry (CV) and square-wave voltammetry (SWV) showed one redox event between E°′ = 250 and 260 mV vs. FcH/FcH+ for 2-5 with all six FcCO2 redox events superimposed. Complexes 6 and 7 show a total of three events in the CV with the oxidations of the nine FcCO2 units occurring in close proximity. Deconvolution of individual redox events correlates well with the mononuclear complex [Bu4N][Gd(O2CFc)4]. UV-Vis/NIR spectroelectrochemical measurements of 7 did not reveal electron transfer between either Fc units, nor the coordinated lanthanides and resembled the absorption behavior of [Bu4N][Tb(O2CFc)4]. DFT (Density Functional Theory) calculations on the B3LYP def2-TZVP level of theory were carried out to assign the order of redox events in 6 showing that the spatial distance towards the most recent redox center, instead of the binding mode, is decisive.
AB - Dinuclear and trinuclear ferrocenylcarboxylato-bridged lanthanide complexes of type [Ln(μO:κ2OO′-O2CFc)(O2CFc)2(H2O)(dmf)]2·(dmf)2 (Ln = Sm (2), Eu (3), Gd (4), Tb (5); Fc = Fe(η5-C5H4)(η5-C5H5)), and novel [Bu4N][Ln3(μ-O2CFc)3(μO:κ2OO′-O2CFc)3(O2CFc)3(μ3-OH)]·[Bu4N]Cl (Ln = Gd (6), Tb (7)) were prepared by the reaction of [LnCl3·6H2O] (synthesis of 2-5) or LnCl3 (synthesis of 6, 7) with FcCO2H (1) in the ratio of 1 : 3. As evidenced by single crystal X-ray structure determination, in 2-5 the lanthanide ions are connected by symmetric FcCO2 units. In addition, two ferrocenylcarboxylato groups are μ-bridged to LnIII. Each LnIII ion is coordinated by nine oxygen donor atoms derived from one H2O, one dmf and three carboxylates. The latter are found in chelating κ2 and bridging μ,κ3 coordination modes. Complexes 6 and 7 assemble three LnIII cores around a central μ3-netting hydroxide and nine FcCO2 entities. A combination of κ2, μ,κ2 and μ,κ3 coordination modes results in an eight-fold coordination sphere for each metal, which is best described as bicapped trigonal prismatic. IR spectroscopy confirms the chelating and bridging motifs. Electrochemical studies of complexes 2-7via cyclic voltammetry (CV) and square-wave voltammetry (SWV) showed one redox event between E°′ = 250 and 260 mV vs. FcH/FcH+ for 2-5 with all six FcCO2 redox events superimposed. Complexes 6 and 7 show a total of three events in the CV with the oxidations of the nine FcCO2 units occurring in close proximity. Deconvolution of individual redox events correlates well with the mononuclear complex [Bu4N][Gd(O2CFc)4]. UV-Vis/NIR spectroelectrochemical measurements of 7 did not reveal electron transfer between either Fc units, nor the coordinated lanthanides and resembled the absorption behavior of [Bu4N][Tb(O2CFc)4]. DFT (Density Functional Theory) calculations on the B3LYP def2-TZVP level of theory were carried out to assign the order of redox events in 6 showing that the spatial distance towards the most recent redox center, instead of the binding mode, is decisive.
UR - http://www.scopus.com/inward/record.url?scp=85178138784&partnerID=8YFLogxK
U2 - 10.1039/d3dt00812f
DO - 10.1039/d3dt00812f
M3 - Article
C2 - 38010135
AN - SCOPUS:85178138784
SN - 1477-9226
VL - 52
SP - 17717
EP - 17730
JO - Dalton Transactions
JF - Dalton Transactions
IS - 47
ER -