Complexes of d- and f-metal Ions with a Redox-Active and Highly Symmetric Truxenone Ligand: Effect of Cations and Coordination on Distortions of Radical Anions and Singlet-Triplet Transitions in Dianions

被引：0

作者：

Krivenko, Kira D. ^{[1
]}

Shestakov, Alexander F. ^{[1
]}

Faraonov, Maxim A. ^{[1
]}

Kuzmin, Alexey V. ^{[2
]}

Khasanov, Salavat S. ^{[2
]}

Otsuka, Akihiro ^{[3
]}

Yamochi, Hideki ^{[3
]}

Kitagawa, Hiroshi ^{[3
]}

Konarev, Dmitri V. ^{[1
]}

机构：

[1] RAS, Fed Res Ctr Problems Chem Phys & Med Chem, Chernogolovka 142432, Moscow Region, Russia

[2] RAS, Inst Solid State Phys, Chernogolovka 142432, Moscow Region, Russia

[3] Kyoto Univ, Grad Sch Sci, Div Chem, Sakyo Ku, Kyoto 6068502, Japan

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2025年

基金：

俄罗斯科学基金会;

关键词：

truxenone; Jahn-Teller distortions; reduction; crystal structure; optical and magnetic properties; STATES; TEMPERATURE; ASSEMBLIES; MAGNETISM;

D O I：

10.1002/ejic.202400760

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Truxenone (Tr) with high C3h symmetry forms crystalline radical anion and dianion salts. The {Bu3MeP+}(Tr & sdot;-) (1) and {Cp*2Co+)}(Tr & sdot;-)& sdot;2 C6H4Cl2 (2) show intense low-energy absorption up to 2000 nm. Calculations predict Jahn-Teller distortions for Tr & sdot;-, which are enhanced by the asymmetric approach of cations to Tr & sdot;-, leading to C=O bond length alternation and EPR signal asymmetry in 2. Two cesium ions form short contacts of 3.07-3.45 & Aring; with oxygen atoms of Tr2- in {Cryptand[2.2.2](Cs+)}2(Tr2-) (3), linking the dianion into a 1D polymer. Calculations suggest a triplet state for the dianion, but the unsymmetric approach of Cs+ to the oxygen atoms of Tr2- stabilizes the singlet ground state. The triplet state is populated above 100 K. An estimated singlet-triplet energy gap is 344 +/- 7 K. Radical anions of Tr & sdot;- coordinate with one d- or f-metal, forming {Cp*2Co+}{TbIII(TMHD)3 & sdot;Tr}-& sdot;1.5 C7H8 (4) and {Cp*2Co+}{MnII(acac)2 & sdot;Tr}-& sdot;2.4 C6H4Cl2 (5) (TMHD is 2,2,6,6-tetramethyl-3,5-heptanedionate; acac is acetylacetonate). Antiferromagnetic TbIII-Tr & sdot;- coupling is observed in 4. The chi MT value of 3.32 emu & sdot;K/mol at 300 K for 5 with high-spin MnII is lower than expected. That indicates a spin state of S=2 owing to the antiparallel alignment of MnII and Tr & sdot;- spins. Strong MnII-Tr & sdot;- coupling arises from the spin density localization on the oxygen coordinated to Mn(II). Complexes with metals demonstrate low-energy absorption with maxima at 1504-1740 nm.

引用

页数：12