Built-in TTF–TCNQ charge-transfer salts in π-stacked pillared layer frameworks

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

“…The target materials, TTF–TCNQ‐built‐in MOFs, were synthesized by the assembly reaction of a paddlewheel‐type dimetal(II, II) complex bearing 2,3,5,6‐tetrafluorobenzoate (=2,3,5,6‐F 4 PhCO 2 − ) ligands (abbreviated as [ M 2 II,II ]; M =Ru, Rh) with a TTF .+ –TCNQ .− salt: (TTF)[{ M 2 II,II (2,3,5,6‐F 4 PhCO 2 ) 4 } 2 (TCNQ)] ( M =Ru, 1 ; Rh, 2 ), which has a three‐dimensional (3D) network motif (Figure a) similar to the compounds with a [{Ru 2 } 2 (TCNQR x )] formula reported previously (TCNQR x =TCNQ derivatives) . The reactions of [Rh 2 II,II ] bearing acetate or ortho ‐chlorobenzoate with TTF .+ –TCNQ .− have provided a 2D layered motif (Figure b), despite having the same formula as 1 and 2 (i.e., [ M 2 II,II ]: TCNQ .− =2:1) . In either case, [ M 2 ] and TCNQ .− units result in a coordination framework with the formula [{ M 2 } 2 (TCNQ)] − ∞ and the TTF .+ cations are coulombically held in pores of the framework (Figure ).…”

“…[33,34] The reactions of [Rh 2 II,II ]b earing acetate or ortho-chlorobenzoate with TTFC + -TCNQC À have provided a2 D layered motif ( Figure 2b), despite having the same formula as 1 and 2 (i.e.,[ M 2 II,II ]: TCNQC À = 2:1). [35] In either case, [M 2 ]a nd TCNQC À units result in ac oordinationf ramework with the formula [{M 2 } 2 (TCNQ)] À 1 and the TTFC + cations are coulombically held in pores of the framework (Figure 2).…”

Ionic Donor–Acceptor Chain Derived from an Electron‐Transfer Reaction of a Paddlewheel‐Type Diruthenium(II, II) Complex and N,N′‐Dicyanoquinonediimine

“…Infrared (IR) spectroscopy is useful for characterizing the oxidation state of polycyano‐organic acceptor units, such as DCNQI and TCNQ derivatives, even when combined in a framework. The (C≡N) stretching modes are characteristically found at 2050–2250 cm −1 , depending on the δ value of the DCNQI δ − /TCNQ δ − . The IR spectrum of 1 was recorded, and a (C≡N) stretching band was observed at 2099 cm −1 (Figure S1 in the Supporting Information), which has lower energy than that of the neutral DMDCNQI unit and neutral D 0 A 0 chain, suggesting the formation of the anionic radical form of DMDCNQI (i.e., DMDCNQI .− ) in 1 .…”

Magnetic Correlation Engineering in Spin‐Sandwiched Layered Magnetic Frameworks

“…[12] Af amily of 2D layered magnetic compounds composed of paddlewheel-type diruthenium(II,II/II,III) complexes ([Ru 2 II,II ]w ith S = 1a nd [Ru 2 II,III ] + with S = 3/2) and ar adical form of 7,7,8,8tetracyano-p-quinodimethane (TCNQ) derivatives( m 4 -TCNQR x C À ) in a2:1 formula [13][14][15][16][17][18][19][20] is an intriguing target fora ttempting systematicc onstruction of hybridized layered systems. In such systems, various types of molecules [21][22][23][24] or ions [25][26][27][28] could be insertedb etween the magnetic layers to result in flexible charge variationsw ithoutc hanging the basic layered framework (Scheme 1a). [29][30][31][32] Among them, p-conjugated inserted molecules were sandwiched between adjacent TCNQ moieties of the layers with a p-stacking mode to form a p-stacked pillared layer framework (p-PLF).…”

“…− ) in a 2:1 formula [13–20] is an intriguing target for attempting systematic construction of hybridized layered systems. In such systems, various types of molecules [21–24] or ions [25–28] could be inserted between the magnetic layers to result in flexible charge variations without changing the basic layered framework (Scheme 1 a). [29–32] Among them, π‐conjugated inserted molecules were sandwiched between adjacent TCNQ moieties of the layers with a π‐stacking mode to form a π‐stacked pillared layer framework (π‐PLF) [33] .…”