Electron-Transferred Donor/Acceptor Ferrimagnet with TC = 91 K in a Layered Assembly of Paddlewheel [Ru2] Units and TCNQ

Kosaka, Wataru; Fukunaga, Hiroki; Miyasaka, Hitoshi

doi:10.1021/acs.inorgchem.5b01776

Cited by 28 publications

(24 citation statements)

References 57 publications

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“…The spins of the [Ru 2 II,II ] ( S = 1) and [Ru 2 II,III ] + ( S = 3/2) moieties interact antiferromagnetically with the radical spin of TCNQ(MeO) 2 •– 41,42 over the layered network forming a ferrimagnetically ordered layer, which is followed by three-dimensional ferrimagnetic ordering with inter-layer ferromagnetic interactions 15,34,36,38–40 . The magnetic transition temperature T C (or T N for antiferromagnetic ordering) for this type of layered magnetic material should be strongly affected by intra-layer exchange interactions between the [Ru 2 ] 0/+ units and TCNQ(MeO) 2 •– , as well as inter-layer dipole interactions 15,36,38–40,43 . Figure 1f shows the temperature dependence of field-cooled dc magnetization (FCM) of 1-solv and 1 in a 1 kOe dc field ( H dc ).…”

Section: Resultsmentioning

confidence: 99%

Gas-responsive porous magnet distinguishes the electron spin of molecular oxygen

et al. 2018

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Gas-sensing materials are becoming increasingly important in our society, requiring high sensitivity to differentiate similar gases like N2 and O2. For the design of such materials, the driving force of electronic host-guest interaction or host-framework changes during the sorption process has commonly been considered necessary; however, this work demonstrates the use of the magnetic characteristics intrinsic to the guest molecules for distinguishing between diamagnetic N2 and CO2 gases from paramagnetic O2 gas. While the uptake of N2 and CO2 leads to an increase in TC through ferrimagnetic behavior, the uptake of O2 results in an O2 pressure-dependent continuous phase change from a ferrimagnet to an antiferromagnet, eventually leading to a novel ferrimagnet with aligned O2 spins following application of a magnetic field. This chameleonic material, the first with switchable magnetism that can discriminate between similarly sized N2 and O2 gases, provides wide scope for new gas-responsive porous magnets.

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Section: Resultsmentioning

confidence: 99%

Gas-responsive porous magnet distinguishes the electron spin of molecular oxygen

et al. 2018

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“…[106] For example, by controlling the charget ransfer in somet wo-dimensional coordination polymers based on electron-donor paddlewheel-type [Ru 2 ] units and electron-acceptor TCNQ derivativesa sl igands it is possible to modulate the magnetic properties towards the design of new molecular magnetsb ased on redox-active MOFs. [107][108][109] TCNQ derivatives have been much less explored as building blocks for the construction of COFs, being used only as doping agentst of orm charge-transfer complexes with thiophene-COFs, [110] or as monomers to self-polymerize forming at riazine-based p-conjugated framework exhibiting room temperature ferromagnetism. [111] In the latter case, stable radi- cals originated by twisting p-bonds around the triazine rings.…”

Section: Tetracyanoquinodimethane (Tcnq)mentioning

confidence: 99%

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the design and construction of crystalline porous frameworks such as metal–organic frameworks (MOFs) and covalent‐organic frameworks (COFs) for applications in electronics. Such porous materials present certain additional advantages such as, for example, an immense structural and functional versatility, combination of porosity with multiple electronic properties and the possibility of tuning their physical properties by post‐synthetic modifications. In this Review, we summarize the main electroactive organic building blocks used in the past few years for the design and construction of functional porous materials (MOFs and COFs) for electronics with special emphasis on their electronic structure and function relationships. The different building blocks have been classified based on the electronic nature and main function of the resulting porous frameworks. The design and synthesis of novel electroactive organic molecules is encouraged towards the construction of functional porous frameworks exhibiting new functions and applications in electronics.

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“…In that situation, the ferrimagnetic ground state could be stabilized by the coupling of the spins of TCNQ .− and [Ru 2 II,II ] through the revived exchange pathway. Indeed, T c =78 K is entirely reasonable in this type of magnetic system …”

Section: Resultsmentioning

confidence: 86%

“…Indeed, T c = 78 Ki se ntirely reasonable in this typeo fm agnetic system. [57,58] The in situ reversiblem agnetic phase switching between PM and FM phases was demonstrated through the rechargeability of the LIB system,f or which am iniaturized LIB cell was inserted into ac ommercials uperconductingq uantum interference device (SQUID). This cell is hereafter called the in situ cell.…”

Section: Resultsmentioning

confidence: 99%

Magnetic Switching by the In Situ Electrochemical Control of Quasi‐Spin‐Peierls Singlet States in a Three‐Dimensional Spin Lattice Incorporating TTF‐TCNQ Salts

Fukunaga

Tonouchi

Taniguchi

et al. 2018

Chemistry A European J

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Magnetic phase switching in a coordination polymer is reported, which is demonstrated by combining two processes: (A) the pre-organization of magnetic/redox-active molecules into a framework, and (B) a post-treatment through electrochemical tuning of the pre-organized molecules. A TTF -TCNQ salt (TTF=tetrathiafulvalene; TCNQ=7,7,8,8-tetracyano-p-quinodimethane) was incorporated into a three-dimensional framework with paddlewheel-type dimetal(II, II) units ([M ]; M=Ru with S=1, 1; and Rh with S=0, 2), where the [M ] and TCNQ units form the coordinating framework, and TTF is located in the pores of framework, forming an irregular π-stacking alternating column with the TCNQ in the framework. In 1, the spins of [Ru ] and TCNQ units make a magnetic correlation through the framework upon decreasing the temperature from 300 K, which is, however, suddenly suppressed below 137 K (=T (1)) by the formation of a spin singlet in the TTF -TCNQ columns, as seen in the spin-Peierls transition (T (2)=200 K). This material was incorporated as a cathode in a Li-ion battery (LIB); a long-range ferrimagnetic correlation was formed through the three-dimensional [{Ru } TCNQ] framework at T =78 K in the discharge process. The reversible magnetic phase switching between the non-volatile ferrimagnetic and paramagnetic states, resulting from the local spin tuning of quasi-spin-Peierls singlet, is demonstrated through the discharge/charge cycling of the LIB.

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Electron-Transferred Donor/Acceptor Ferrimagnet with T_C = 91 K in a Layered Assembly of Paddlewheel [Ru₂] Units and TCNQ

Cited by 28 publications

References 57 publications

Gas-responsive porous magnet distinguishes the electron spin of molecular oxygen

Gas-responsive porous magnet distinguishes the electron spin of molecular oxygen

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Magnetic Switching by the In Situ Electrochemical Control of Quasi‐Spin‐Peierls Singlet States in a Three‐Dimensional Spin Lattice Incorporating TTF‐TCNQ Salts

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