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

Abstract

A new ionic donor-acceptor (D A ) chain compound, [{Ru (2,6-(CF ) PhCO ) (p-PhPhCO ) }DMDCNQI] (1; 2,6-(CF ) PhCO =2,6-bis(trifluoromethyl)benzoate; p-PhPhCO =4-biphenylcarboxylate; DMDCNQI=2,5-dimethyl-N,N'-dicyanoquinonediimine) was isolated and structurally characterized. It represents the first of this type of ionic chain compounds.

A Host–Guest Electron Transfer Mechanism for Magnetic and Electronic Modifications in a Redox‐Active Metal–Organic Framework

“…]). The coupling constant, J 1 , is considerably larger than the experimentally obtained equivalent in one-dimensional chain systems (J Ru2-Rad � À 100 cm À 1 ), [49][50][51] because of both the small cluster model and the employed functional set; [52,53] however, it is consistent with the fact that it is strongly antiferromagnetic. This coupling clearly originates from the significant orbital overlap between the π* orbital of the [Ru 2…”

Ionicity Diagrams for Electron-Donor and -Acceptor Metal–Organic Frameworks: DA Chains and D2A Layers Obtained from Paddlewheel-Type Diruthenium(II,II) Complexes and Polycyano-Organic Acceptors

“…All of the compounds formed a one-dimensional chain feature, in which the [Ru 2 ] units and the DCNQI/TCNQ derivatives were alternately arranged and acted as coordination-acceptor and bidentate (μ 2 ) and coordination-donor building blocks, respectively. N-1 and N-3 belong to the DCNQI-bridging family, along with [Ru 2 (2,3,5,6-F 4 PhCO 2 ) 4 DOMDCNQI]·4­( p -xylene) ( N-2 ), [Ru 2 (F 5 PhCO 2 ) 4 DMDCNQI]·4­( p -xylene) ( N-4 ), [{Ru 2 (2,6-(CF 3 ) 2 PhCO 2 ) 2 ( p -PhPhCO 2 ) 2 }­DMDCNQI] ( I-2 ), and [Ru 2 (2,3,5,6-F 4 PhCO 2 ) 4 DMDCNQI]·2­( p -xylene) ( NI-1 ) (Figures S4–S7). Although TCNQ derivatives could act as tetradentate (μ 4 ) bridging ligands in the D 2 A system, ,− the corresponding moiety in N-5 – N-17 , as well as in [{Ru 2 (2-MeO-4-ClPhCO 2 ) 4 }­(BTDA-TCNQ)]·2.5­(benzene) ( I-1 ) and [Ru 2 (3,4-Cl 2 PhCO 2 ) 4 TCNQ­(EtO) 2 ]·DCE ( NI-2 ), acted as a linear-type μ 2 ligand in a trans -coordinating mode, similar to the behavior of a DCNQI ligand (Scheme S1 and Figures S8–S20).…”

“…A plot of Δ E H–L (DA) vs Δ E 1/2 (DA) for all DA − and D 2 A ,− series reported to date, including the present DA chains, is shown in Figure a and displays a linear least-squares fitted line (LS-FL). The respective plots for the DA chains and the D 2 A systems composed of D 2 A layers ,− and D 2 A finite network , were extracted into Figure b,c, respectively, from Figure a (the linear LS-FL is fixed from Figure a).…”

“…In this study, we constructed 15 one-dimensional chains obtained from the reactions of [Ru 2 II,II ] complexes and DCNQI/TCNQ derivatives. An ionicity diagram of Δ E H‑L (DA) vs Δ E 1/2 (DA) was empirically made for the DA series, including previously reported neutral D 0 A 0 compounds, , ionic D + A – compounds, , and thermally charged variable compounds , (Scheme S1). Furthermore, an ionicity diagram for the D 2 A system is characterized by comparing it to the ionicity diagram of the DA chains.…”

“…DCNQI •− /TCNQ ] + units. 24,25 Figure 2 shows the correlation between the Ru−O eq bond lengths and DA chain ρ values, where the distinct classification of the bond distance distribution is dependent on the electronic state of the DA chains. Notably, the electronic state of thermally charged variable compounds, i.e., N−I transition systems, varies at the transition temperature (T 1/2 ) but is neutral when T > T 1/2 and ionic when T < T 1/2 .…”